Nafion is commonly used as a catalyst binder in many types of electrochemical cells, but less expensive binders are needed for the cathodes in microbial electrolysis cells (MECs) which are operated in neutral pH buffers, and reverse electrodialysis stacks (RED),which use thermolytic solutions such as ammonium bicarbonate. Six different binders were examined based on differences in ion exchange properties (anionic: Nafion, BPSH20, BPSH40, S-Radel; cationic: Q-Radel; and neutral: Radel, BAEH) and hydrophobicity based on water uptake (0%, Radel; 17–56% for the other binders). BPSH40 had similar performance to Nafion based on steady-state polarization single electrode experiments in a neutral pH phosphate buffer, and slightly better performance in ammonium bicarbonate. Three different Mo-based catalysts were examined as alternatives to Pt, with MoB showing the best performance under steady-state polarization. In MECs, MoB/BPSH40 performed similarly to Pt with Nafion or Radel binders. The main distinguishing feature of the BPSH40 was that it is very hydrophilic, and thus it had a greater water content (56%) than the other binders (0–44%). These results suggest the binders for hydrogen evolution in MECs should be designed to have a high water content without sacrificing ionic or electronic conductivity in the electrode.