The processing of solar to hydrogen energy conversion semiconductor devices strongly relies on the charge mobility and reactivity of hydrogen evolution reactions. Intrinsic defects induced polaron has been applied on the surface of Cu2O polyhedron nanoparticles to modulate the hydrogen cations reduction and hydrogen evolution reaction by high charge mobility and H atoms high selective of specific external terminated atoms. With the polaron surface state applied on truncated octahedron Cu2O nanoparticle photocathode, the water splitting efficiency achieved 2.12 % at 0.2 V working bias. The hydrogen generation rate is as high as 9.38 L/m2⋅h. Besides, under 1.23 V applied bias, at 1 atm pressure and room temperature, there are over 64 L hydrogen gases are generated in only one hour, and the hydrogen generation rate is as high as 65.39 L/m2⋅h. During this study, a defined p typed polaron surface state for raising charge mobility and hydrogen evolution in solar to hydrogen conversion system is illustrated, which provides the reliable application in related photon to electron conversion and high performance energy conversion devices.