Efficient hydrogen production through an electrocatalytic hydrogen evolution reaction (HER) represents an attractive technology for addressing global energy challenges. Toward this end, the development of high-performance HER catalysts represents a critical first step. Herein, high-valence PtClxOy clusters are dispersed on Y2O3 nanoparticle surfaces via an ambient impregnation method at a Pt loading of up to 21.31 wt % using H2PtCl6 as the precursor. Among the series, the PtClxOy/Y2O3-4 sample, with a Pt content of 5.84 wt %, exhibits the best HER activity in alkaline media with a low overpotential of -26 mV at 10 A cm-2. This is ascribed to the synergistic interactions between the Pt clusters and Y2O3 as well as the surrounding O and Cl atoms that impact the energetics of hydrogen adsorption, as revealed by computational studies based on density functional theory calculations. Results from this study underscore the impact of electronic manipulation on the electrocatalytic activity of nanocomposites for electrochemical energy technologies.