/ 是不是连接错了，应该MOSI -- MISO，MISO -- MOSI连接。

说到点上了，你看他怎么接的“（NSS两脚相连,CLK两片脚相连,MOSI两片脚相连,MISO两片脚相连”，肯定不行的啦

#include"stm32f10x_lib.h"

#define BufferSize 32

u8 SPI1_Buffer_Tx[BufferSize] = {0x01,0x02,0x03,0x04,0x05,0x06,0x07,0x08,0x09,
                                 0x0A,0x0B,0x0C,0x0D,0x0E,0x0F,0x10,0x11,0x12,
                                 0x13,0x14,0x15,0x16,0x17,0x18,0x19,0x1A,0x1B,
                                 0x1C,0x1D,0x1E,0x1F,0x20};
u8 SPI2_Buffer_Tx[BufferSize] = {0x51,0x52,0x53,0x54,0x55,0x56,0x57,0x58,0x59,
                                 0x5A,0x5B,0x5C,0x5D,0x5E,0x5F,0x60,0x61,0x62,
                                 0x63,0x64,0x65,0x66,0x67,0x68,0x69,0x6A,0x6B,
                                 0x6C,0x6D,0x6E,0x6F,0x70};

u8 SPI1_Buffer_Rx[BufferSize], SPI2_Buffer_Rx[BufferSize];
u8 Tx_Idx = 0, Rx_Idx = 0, k = 0;

SPI_InitTypeDef   SPI_InitStructure;

void RCC_Configuration(void);
void NVIC_Configuration(void);
void SPI_Configuration(void);
void GPIO_Configuration(void);

int main(void)
{
#ifdef debug
  debug();
#endif
  RCC_Configuration();
  NVIC_Configuration();
  SPI_Configuration();
  GPIO_Configuration();
  while(1)
  {
     while(Tx_Idx<BufferSize)  //BufferSize==32
  {
    /* Wait for SPI1 Tx buffer empty */
    while(SPI_I2S_GetFlagStatus(SPI1, SPI_I2S_FLAG_TXE)==RESET);
    /* 数据发送寄存器为空 */
    SPI_I2S_SendData(SPI2, SPI2_Buffer_Tx[Tx_Idx]);       
    /* SPI2主模式发送 */
    SPI_I2S_SendData(SPI1, SPI1_Buffer_Tx[Tx_Idx++]);     
    /* Wait for SPI2 data reception */
    while(SPI_I2S_GetFlagStatus(SPI2, SPI_I2S_FLAG_RXNE)==RESET);
    /* Read SPI2 received data */
    SPI2_Buffer_Rx[Rx_Idx] = SPI_I2S_ReceiveData(SPI2);
    /* Wait for SPI1 data reception */
    while(SPI_I2S_GetFlagStatus(SPI1, SPI_I2S_FLAG_RXNE)==RESET);
    /* Read SPI1 received data */
    SPI1_Buffer_Rx[Rx_Idx++] = SPI_I2S_ReceiveData(SPI1);                 
  }
  /* 2nd phase: SPI1 Slave and SPI2 Master */  
  /* SPI1 Re-configuration ---------------------------------------------------*/
  SPI_InitStructure.SPI_Mode = SPI_Mode_Slave;
  SPI_Init(SPI1, &SPI_InitStructure);

  /* SPI2 Re-configuration ---------------------------------------------------*/
  SPI_InitStructure.SPI_Mode = SPI_Mode_Master;
  SPI_Init(SPI2, &SPI_InitStructure);

  /* Reset Tx_Idx, Rx_Idx indexes and receive tables values */
  Tx_Idx=0;
  Rx_Idx=0;
  for(k=0; k<BufferSize; k++)  SPI2_Buffer_Rx[k]=0;
  for(k=0; k<BufferSize; k++)  SPI1_Buffer_Rx[k]=0;

  /* Transfer procedure */
  while(Tx_Idx<BufferSize)        //BufferSize==32
  {
    /* 检测指定的SPI标志位设置是否 */
    while(SPI_I2S_GetFlagStatus(SPI2, SPI_I2S_FLAG_TXE)==RESET);
    /* 通过SPI1发送一个数据 */
    SPI_I2S_SendData(SPI1, SPI1_Buffer_Tx[Tx_Idx]);
    /* 通过SPI2发送一个数据*/
    SPI_I2S_SendData(SPI2, SPI2_Buffer_Tx[Tx_Idx++]);
    /* 检测指定的SPI标志位设置是否 */
    while(SPI_I2S_GetFlagStatus(SPI1, SPI_I2S_FLAG_RXNE)==RESET);
    /* Buffer_Rx[Rx_Tdx]接受SPI2的数据 */
    SPI1_Buffer_Rx[Rx_Idx] = SPI_I2S_ReceiveData(SPI1);
    /* Wait for SPI2 data reception */
    while(SPI_I2S_GetFlagStatus(SPI2, SPI_I2S_FLAG_RXNE)==RESET);
    /* Buffer_Rx[Rx_Tdx]接受SPI1的数据*/
    SPI2_Buffer_Rx[Rx_Idx++] = SPI_I2S_ReceiveData(SPI2);
  }

  /* Check the corectness of written dada */
  while(1)
  {
  }

  }
}

void RCC_Configuration(void)
{
  ErrorStatus HSEStartUpStatus;
  /* RCC system reset(for debug purpose) */
  RCC_DeInit();

  /* Enable HSE */
  RCC_HSEConfig(RCC_HSE_ON);

  /* Wait till HSE is ready */
  HSEStartUpStatus = RCC_WaitForHSEStartUp();

  if(HSEStartUpStatus == SUCCESS)
  {
    /* HCLK = SYSCLK */
    RCC_HCLKConfig(RCC_SYSCLK_Div1);
  
    /* PCLK2 = HCLK/2 */
    RCC_PCLK2Config(RCC_HCLK_Div2);

    /* PCLK1 = HCLK/2 */
    RCC_PCLK1Config(RCC_HCLK_Div2);

    /* Flash 2 wait state */
    FLASH_SetLatency(FLASH_Latency_2);
    /* Enable Prefetch Buffer */
    FLASH_PrefetchBufferCmd(FLASH_PrefetchBuffer_Enable);

    /* PLLCLK = 8MHz * 9 = 72 MHz */
    RCC_PLLConfig(RCC_PLLSource_HSE_Div1, RCC_PLLMul_9);

    /* Enable PLL */
    RCC_PLLCmd(ENABLE);

    /* Wait till PLL is ready */
    while(RCC_GetFlagStatus(RCC_FLAG_PLLRDY) == RESET)
    {
    }

    /* Select PLL as system clock source */
    RCC_SYSCLKConfig(RCC_SYSCLKSource_PLLCLK);

    /* Wait till PLL is used as system clock source */
    while(RCC_GetSYSCLKSource() != 0x08)
    {
    }
  }
   RCC_APB2PeriphClockCmd(RCC_APB2Periph_GPIOA|RCC_APB2Periph_GPIOB|RCC_APB2Periph_SPI1,ENABLE);
   /* SPI2 Periph clock enable */
   RCC_APB1PeriphClockCmd(RCC_APB1Periph_SPI2,ENABLE);
}

void NVIC_Configuration(void)
{
#ifdef  VECT_TAB_RAM  
  /* Set the Vector Table base location at 0x20000000 */
  NVIC_SetVectorTable(NVIC_VectTab_RAM, 0x0);
#else  /* VECT_TAB_FLASH  */
  /* Set the Vector Table base location at 0x08000000 */
  NVIC_SetVectorTable(NVIC_VectTab_FLASH, 0x0);   
#endif
}


void SPI_Configuration(void)
{
  SPI_Cmd(SPI1, DISABLE); //先禁能,才能改变MODE模式
  SPI_Cmd(SPI2, DISABLE);
  SPI_InitStructure.SPI_Direction = SPI_Direction_2Lines_FullDuplex;  //两线全双工
  SPI_InitStructure.SPI_Mode = SPI_Mode_Master;          //主模式
  SPI_InitStructure.SPI_DataSize = SPI_DataSize_8b;  //8位
  SPI_InitStructure.SPI_CPOL = SPI_CPOL_Low;        //CPOL=0时钟悬空低
  SPI_InitStructure.SPI_CPHA = SPI_CPHA_2Edge; //CPHA=1 数据在第二个沿捕获
  SPI_InitStructure.SPI_NSS = SPI_NSS_Soft;        //或hard模式
  SPI_InitStructure.SPI_BaudRatePrescaler = SPI_BaudRatePrescaler_4;  //4分频
  SPI_InitStructure.SPI_FirstBit = SPI_FirstBit_LSB;   //高位在前
  SPI_InitStructure.SPI_CRCPolynomial = 7;           //CRC7（效验位7）
  SPI_Init(SPI1, &SPI_InitStructure);          //SPI1为主模式
  /* SPI2 Config -------------------------------------------------------------*/
  SPI_InitStructure.SPI_Mode = SPI_Mode_Slave;
  SPI_Init(SPI2, &SPI_InitStructure);          //SPI2为从模式
  /* Enable SPI1 */
  SPI_Cmd(SPI1, ENABLE);   //SPI1使能
  /* Enable SPI2 */
  SPI_Cmd(SPI2, ENABLE);   //SPI2使能
}

void GPIO_Configuration(void)
{
  GPIO_InitTypeDef GPIO_InitStructure;
  /* Configure SPI1 pins: SCK, MISO and MOSI ---------------------------------*/
  GPIO_InitStructure.GPIO_Pin = GPIO_Pin_5 | GPIO_Pin_6 | GPIO_Pin_7;
  GPIO_InitStructure.GPIO_Speed = GPIO_Speed_50MHz;
  GPIO_InitStructure.GPIO_Mode = GPIO_Mode_AF_PP; //复用推挽输出
  GPIO_Init(GPIOA, &GPIO_InitStructure);
  /* Configure SPI2 pins: SCK, MISO and MOSI ---------------------------------*/
  GPIO_InitStructure.GPIO_Pin = GPIO_Pin_13 | GPIO_Pin_14 | GPIO_Pin_15;
  GPIO_InitStructure.GPIO_Speed = GPIO_Speed_50MHz;
  GPIO_InitStructure.GPIO_Mode = GPIO_Mode_AF_PP; //复用推挽输出
  GPIO_Init(GPIOB, &GPIO_InitStructure);
}