In this paper, we suggest a new method for cryptanalysis of the basic structures of the block ciphers having SP network structure. The concept of the substitution difference is introduced and the distribution characteristics of substitution distances in an S-box is developed. This gives clues for cryptanalysis of the cipher. We then examine if this method is applicable to cryptanalysis of Rijndael. We present the method for cryptanalysis of the first round of Rijndael including the initial Round-Key addition part in order to illustrate our new method.