Polypyrrole (Ppy) was successfully introduced into methyl substituted sulfonated poly(ether ether ketone) (SPEEK) membranes by polymerization in SPEEK solutions to improve their methanol resistance. Uniform polypyrrole (Ppy) distributed composite membranes were formed by this method by the interaction between SPEEK and Ppy. The properties of the composite membranes were characterized in detail. The composite membranes show very good proton conductive capability (25°C: 0.05–0.06scm−1) and good methanol resistance (25°C: 5.3×10−7–1.1×10−6 cm2 s−1).The methanol diffusion coefficients of composite membranes are much lower than that of pure SPEEK membranes (1.5×10−6 cm2 s−1). The composite membranes show very good potential usage in direct methanol fuel cells (DMFCs).