To provide a process for forming a catalyst layer whereby defects such as cracks are scarcely formed in the catalyst layer, and the bond strength is high at the interface between the catalyst layer and a reinforcing layer and at the interface between the catalyst layer and a polymer electrolyte membrane; and a process for producing a membrane/electrode assembly for a polymer electrolyte fuel cell, which is capable of exhibiting high power generation performance even under a low humidity condition and has sufficient mechanical strength and dimensional stability and which has excellent durability even in an environment where humidification and drying, etc. are repeated.In the production of a membrane/electrode assembly 10, a first catalyst layer 22 (a second catalyst layer 34) is formed by a process comprising steps (a) and (b). (a) A step of applying a coating fluid comprising a catalyst and an ion-exchange resin, on a substrate to form a coating fluid layer. (b) A step of disposing a reinforcing layer 24 (34) on the coating fluid layer formed in the step (a) and then, drying the coating fluid layer to form a first catalyst layer 22 (a second catalyst layer 34).