This study aims to determine the optimized hydrogen–oxygen stoichiometric ratio for power performance improvement in a large-scale proton exchange membrane fuel cell (PEMFC) stack by analyzing the characteristics of internal heat and mass distributions. The power performance of a large-scale PEMFC stack consisting of the designed stack cells with the counter flow directions of hydrogen and oxygen and a coolant flow channel was experimentally evaluated. Temperatures in the central stack cell were monitored. The coupled numerical simulation model was built to analyze the power performance as well as heat and mass distribution characteristics inside a stack cell. It was found that the greatest power performance of the PEMFC stack occurred at a specific hydrogen–oxygen stoichiometric ratio, and this performance had good uniformities of the temperature and water mass fraction distributions at the proton exchange membrane (PEM). The distribution characteristics of the hydrogen and oxygen mass fractions at the interfaces between the gas diffusion layer (GDL) and the catalytic layer (CL) due to the diffusion effect were analyzed. The mechanism of enhancing power performance from an electrochemical reaction was revealed by the greater gas distribution uniformities. Furthermore, a parameter of energy conversion ratio was employed to quantify the hydrogen utilization degree.