Homogeneuosly sulfonated poly(styrene) (SPS) was prepared with various concentration of sulfonic acid groups in the base polymer. Membranes cast from these materials were investigated in relation to proton conductivity and methanol permeability in the temperature range from 20°C to 60°C. It was found that both these properties increase as the polymer is increasingly sulfonated, with abrupt jumps occurring at a concentration of sulfonic acid groups of about 15 mol%. The most extensively sulfonated membrane exhibited conductivity equal to that of Nafion. As a consequence, this membrane material is potentially an appealing alternative to the very expensive Nafion, for a number of electrochemical applications. For the membrane with the highest degree of sulfonation we measured a methanol permeability about 70% smaller than for Nafion. This characteristic is especially desirable in applications related to the direct methanol fuel cell (DMFC).