Highly methanol-tolerant CoSe nanoparticles supported on different carbon substrates were synthesized by microwave heating of glycerol solutions of cobalt(II) acetate and sodium selenite at different Se/Co mole ratios in the presence of different concentrations of acetic acid and ammonia. The resulting CoSe catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution in the presence of methanol. The ORR activity of the catalyst was increased by increasing its Se content up to 50 mol%. The presence of acetic acid or ammonia in the synthesis solution significantly affects the electrocatalytic performance of the CoSe catalyst; highest activity was observed when the catalyst was synthesized at NH3/Co(II) mole ratio of 6. Among the catalysts prepared on different supports including carbon black (Vulcan XC- 72R), and nanoporous carbons synthesized from resorcinolformaldehyde and phloroglucinol-formaldehyde resins, the one supported on the carbon prepared from the last resin exhibited highest electrocatalytic activity for ORR.