Photocatalytic water splitting for hydrogen generation is a significant pathway for sustainable energy conversion and production. The photocatalysts with a Z-scheme water splitting charge transfer pathway is superior due to the good separation and migration ability of photoexcited charge carriers. Herein, Co3O4/g-C3N4 photocatalysts with Z-scheme charge transfer pathway were successfully constructed by an electrostatic interaction-annealing method. The as-prepared Co3O4/g-C3N4 ultra-thin nanosheets were tested and analyzed by XRD, EA, ICP, SEM, TEM, AFM, XPS, UV-Vis DRS, PL and photoelectrochemical measurements. Moreover, the influences of fabrication parameters on performance of Co3O4/g-C3N4 catalysts were investigated, and 0.5% Co3O4/g-C3N4 exhibited the optimal activity. Based on the characterization and catalytic performance, the Z-scheme charge transfer pathway of Co3O4/g-C3N4 was established and put forward. To further improve the catalytic performance of Co3O4/g-C3N4, 0.5% Pt was added as a co-catalyst. The obtained Pt/0.5% Co3O4/g-C3N4 was recyclable and remained the original catalytic water splitting performance within 20 h. The modification of Co3O4 and Pt improved the separation and migration of e− and h+, and induced the increased hydrogen evolution rate of g-C3N4.