Hydrogen generation by photocatalytic water splitting has attained more and more research interests in the recent years since the solar energy can be directly transferred and stored as hydrogen. However, the search for a high-efficiency photocatalyst for water splitting is a really challenge. In this paper, we designed a novel 2D material-based van der Waals heterostructure (vdWH) composed by g-GaN and BSe, which is thermally stable at room temperature. The g-GaN/BSe vdWH has suitable band-edge positions for the oxidation and reduction reactions of water splitting at pH 0 and 7. The carrier mobility of this heterostructure is high, indicating the effective occurrence of reactions for water splitting. The g-GaN/BSe vdWH also possesses a type-II band alignment, which can promote the separation of the photogenerated electron-hole pairs constantly. Moreover, a large built-in electric field can be established at the interface, which will further prevent the recombination of photogenerated charges. In addition, the g-GaN/BSe vdWH also exhibits outstanding sunlight-absorption ability, and the biaxial strain can further enhance this ability. Thus, we conclude that the g-GaN/BSe vdWH can act as a high-efficiency photocatalyst for water splitting.