Hydrogen production via a directly coupled solar‐proton exchange membrane (PEM) electrolysis system using aqueous methanol instead of water was investigated. The effect of load matching and methanol concentration on hydrogen production rates, electrolysis efficiency, and solar‐hydrogen efficiency was evaluated. The electrolysis efficiencies were subsequently used in simulation studies to estimate production costs in scaled‐up systems. The results demonstrate that the added hydrogen production associated with the methanol solutions leads to favorable hydrogen production costs at smaller scales.