Abstract Eighteen Z‐X‐Y‐OTNB + type dipeptides, four Z‐Val‐Cys(Bzl)‐X‐OTMB tripeptides and a tetrapeptide Z‐Val‐Cys(Bzl)‐Cys(Bzl)‐Asn‐OTMB have been synthesized by papain‐catalyzed reaction in reasonable yield after recystallization. Z‐DL‐Ala‐OH has been resolved through papain‐catalyzed synthesis of Z‐L‐Ala‐Leu‐OTMB with an optical purity as high as 98.6%. These results show that papain is a good catalyst for oligopeptide synthesis.