We report the preparation of phosphoric acid doped poly(2,5-benzimidazole) (ABPBI) membranes for PEMFC by simultaneously doping and casting from a poly(2,5-benzimidazole)/phosphoric acid/methanesulfonic acid (MSA) solution. The evaporation of MSA yields a very homogeneous membrane having a better controlled composition, avoiding the use of solvent-intensive procedures. Membranes have been prepared with contents of up to 3.0H3PO 4 molecules per ABPBI repeating unit. These membranes achieve a maximum conductivity of 1.5 × 10-2 S cm-1 at temperatures as high as 180°C in dry conditions. These ABPBI membranes are more conveniently prepared than those conventionally formed and doped in separate steps while featuring comparable conductivities (ABPBI × 2.7H3PO4 prepared by the soaking method showed a conductivity of 2.5 × 10-2 S cm-1 at 180°C in dry conditions).