Polystyrene-supported N-phenyl-N-acyl sulfonamide resin was prepared by reacting polystyrene sulfonyl chloride resin with aniline and acylating in pyridine with either acid chlorides or anhydrides. Then, this resin was utilized as a new type of acyl transfer reagent to synthesize the amide library. It was approved to be a more effective acyl transfer reagent with higher amide yields than the polystyrene-supported N-methyl-N-acyl sulfonamide resin and N-benzyl-N-acyl sulfonamide resin. When the phenyl group bonded to the N atom on N-phenyl-N-acyl sulfonamide resin was substituted by the electron withdrawing group or electron donating group, a decreasing amide yield was obtained. N-phenyl-N-acyl sulfonamide resin could be regenerated many times.