To provide a membrane/electrode assembly for polymer electrolyte fuel cells, which is capable of providing high power generation performance even under a low humidity condition and has sufficient mechanical strength and dimensional stability, and which has an excellent durability even in an environment where moistening and drying are repeated, and a polymer electrolyte fuel cell which is capable of providing high power generation performance even under a low humidity condition. A membrane/electrode assembly 10 is used, which comprises a cathode 20 having a catalyst layer 22, an anode 30 having a catalyst layer 32, and a polymer electrolyte membrane 40 interposed between the catalyst layer 22 of the cathode 20 and the catalyst layer 32 of the anode 30, wherein at least one of the cathode 20 and the anode 30 further has a reinforcing layer 26 comprising a porous sheet-form reinforcing material made of a polymer, and an electrically conductive fiber.