A critical determinant of solar-driven water splitting efficiency is the kinetic profile of the O-2 evolving catalyst (OEC). We now report the kinetic profiles of water splitting by a self-assembled nickel-borate (NiBi) OEC. Mechanistic studies of anodized films of NiBi exhibit the low Tafel slope of 2.3 X RT/2F (30 mV/decade at 25 degrees C). This Tafel slope together with an inverse third order rate dependence on H+ activity establishes NiBi as an ideal catalyst to be used in the construction of photoelectrochemical devices for water splitting. In contrast, nonanodized NiBi films display significantly poorer activity relative to their anodized congeners that we attribute to a more sluggish electron transfer from the catalyst resting state. Borate is shown to play two ostensibly antagonistic roles in OEC activity: as a promulgator of catalyst activity by enabling proton-coupled electron transfer (PCET) and as an inhibitor in its role as an adsorbate of active sites. By defining the nature of the PCET pre-equilibrium that occurs during turnover, trends in catalyst activity may be completely reversed at intermediate pH as compared to those at pH extremes. These results highlight the critical role of PCET pre-equilibria in catalyst self-assembly and turnover, and accordingly suggest a reassessment in how OEC activities of different catalysts are compared and rationalized.