Photoelectrocatalytic (PEC) technique for hydrogen evolution from water splitting and pollutant degradation is one of the most sustainable and environmental approaches for wastewater treatment and energy regeneration. Herein, a porous graphitic carbon nitride (g-C3N4)/reduction graphene oxide (rGO) structure (CNG) is constructed via a solvothermal approach. By using a facile electrophoretic deposition method, CNG is deposited on nickel (Ni) foam with the formation of highly active CNG-Ni foam photoanode. rGO were utilized to load g-C3N4 , and also acts as the bridge for accelerating the rate of electron transfer from g-C(3)N(4)to Ni foam. The resulted photoanode exhibits an excellent photoelectrochemical performance for synergistic pollutant degradation and H-2 evolution under visible light irradiation (lambda > 420 nm). Such excellent PEC activity is attributed to the strong visible-light absorption and fast electron transmission of the as-obtained photoanode. The visible light-driven photocurrent value of the optimal photoanode can be well maintained up to 24 h, indicating its high stability during the PEC process. This work also shows significance for paving a facile route to fabricating highly active photoelectrodes for environmental and energy applications.