The synthesis of a molecularly imprinted polymer (MIP) composed of tetraethoxysilane (TEOS) for recognizing sulfonamides by sol-gel process is developed. The MIP's preparation conditions, the H(2)O/Si molar ratios (R), pH value of the competition solution, and the calcination process are discussed. The competition experiments of the MIP for template (sulfamethazine, SMZ) and analogue (sulfamethoxazole, SMO) are performed by High-Performance Liquid Chromatography (HPLC). The results show that the selectivity of the competition solution with pH = 7.4 is higher than those with pH = 4.6. In addition, the selectivity of SMZ increases, while the calcination time and the calcination temperatures increase. Moreover, the selectivity of the MIP (53.3) is approximately seven times greater than that of the non-imprinted polymer (NIP) (8.32) under optimum preparation conditions.