Bottom-up synthesis of porous NiMo alloy reduced by NiMoO4 nanofibers was systematically investigated to fabricate non-noble metal porous electrodes for hydrogen production. The different annealing temperatures of NiMoO4 nanofibers under hydrogen atmosphere reveal that the 950 °C annealing temperature is a key to produce bicontinuous porous NiMo alloy without oxide phases. The porous NiMo alloy as cathodes in electrical water splitting demonstrates not only almost identical catalytic activity with commercial Pt/C in 1.0 M KOH solution, but also superb stability for 12 days at an electrode potential of −200 mV (v.s. RHE).