The dark electrocatalytic and light photocathodic hydrogen evolution properties of Ni, Ni-Mo alloys, and Pt on Si electrodes have been measured, to assess the viability of earth-abundant electrocatalysts for integrated, semiconductor coupled fuel formation. In the dark, the activities of these catalysts deposited on degenerately doped p+-Si electrodes increased in the order Ni Ni-Mo less-than-or-equal Pt. Ni-Mo deposited on degenerately doped Si microwires exhibited activity that was very similar to that of Pt deposited by metal evaporation on planar Si electrodes. Under 100 mW cm-2 of Air Mass 1.5 solar simulation, the energy conversion efficiencies of p-type Si/catalyst photoelectrodes ranged from 0.2-1%, and increased in the order Ni approximate Ni-Mo Pt, due to somewhat lower photovoltages and photocurrents for p-Si/Ni-Mo relative to p-Si/Ni and p-Si/Pt photoelectrodes. Deposition of the catalysts onto microwire arrays resulted in higher apparent catalytic activities and similar photoelectrode efficiencies than were observed on planar p-Si photocathodes, despite lower light absorption by p-Si in the microwire structures.