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Photocatalytic water splitting to obtain hydrogen energy can transform low‐density solar to high density, new and clean energy in a clean way, which is one of the ideal ways to solve the energy crisis and environmental pollution. In this paper, The CoxP/hollow porous C3N4 composite photocatalytic material was synthesized by simple methods. The photocatalytic hydrogen production rate of CoxP/hollow porous C3N4 reaches 1602 μmol g−1 h−1, which is 151 times of that of pure C3N4. The reasons for the high photocatalytic H2 evolution activity of CoxP/hollow porous C3N4 could be summarized as follows: (1) the hollow and porous structure of C3N4 shows higher light capture efficiency, larger specific surface area and more surface active sites. (2) metalloid CoxP loaded forms the Schottky contact with C3N4, which improves the photogenerated charges separation efficiency of C3N4, prolongs the photogenerated charges lifetime and improves the photocatalytic H2 evolution activity of C3N4. (3) The higher conductivity of metalloid CoxP and the lower overpotential of hydrogen production are other reasons for the higher activity of photocatalytic hydrogen production of CoxP/hollow porous C3N4. This work provides an important role for the design of efficient, stable, and efficient construction of photocatalysts for solar energy conversion. [ABSTRACT FROM AUTHOR]