A high‐efficiency photocatalyst is critical for water splitting by solar light. Herein, via first principles calculations, the 2D polarized GeS/MoSe2 van der Waals (vdW) heterostructure is proposed as an efficient water redox photocatalyst. The performance of GeS/MoSe2 heterostructure is better than isolated materials, as the properties of GeS monolayer and MoSe2 monolayer are complementary by forming vdW heterostructure. GeS/MoSe2 heterostructure possesses suitable bandgap, dipole‐induced internal electric field, and excellent solar absorption performance. The band alignments of GeS/MoSe2 heterostructure are suitable compared with the redox potential of water. It is feasible to tune the optoelectronic properties and enhance photocatalytic activity of GeS/MoSe2 heterostructure via strain engineering. Biaxial compressive strain range from −2% to −3% induces the direct bandgap characteristic in GeS/MoSe2 heterostructure. The results suggest that 2D polarized GeS/MoSe2 vdW heterostructure is a potential novel high‐efficiency photocatalyst for water splitting under a wide range of spectra from ultraviolet to near infrared.