This study tackles the core issues associated with near-neutral pH water splitting, particularly regarding electrolyte engineering in the electrocatalysis and product cross-over. We demonstrate that solute engineering has a major impact on water splitting electrocatalysis because the diffusion component, often not well integrated into performance descriptions, largely determines the overall performance. The hydrogen evolution reaction (HER) was investigated on Pt, Ni and NiMo catalysts in various concentrations of cations (Li+, K+, Na+) and anions (H2PO4−, HPO42−, PO43− and HCO3−) to describe its performance by quantifying kinetics, diffusion and solution resistance. In fact, the choice of electrolyte in terms of its identity and activity drastically altered the HER rate and oxygen mass-transport flux at near-neutral pH. Electrolyte properties (activity coefficient, kinematic viscosity and diffusion coefficient) accurately described the diffusion contribution, which can be easily isolated when a highly active Pt catalyst was used for the HER. By analyzing these properties, we maximized the HER rate on the Pt by tuning the solute concentration (typically 1.5 – 2.0 M). Moreover, the kinematic viscosity and oxygen solubility in such densely buffered conditions governed the oxygen mass-transport flux in the electrolyte, which in turn tuned the cross-over flux. At near-neutral pH, as high as 90 % selectivity toward the HER was achieved even under an oxygen saturated condition, where only a 40 mV overpotential was needed to achieve 10 mA cm−2 for the HER. This information can be regarded as an important milestone for achieving a highly efficient water splitting system at near-neutral pH.