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The graphene oxide @nickel phosphate (GO:NPO) nanocomposites (NCs) are prepared by using a one-pot in-situ solar energy assisted method by varying GO:NPO ratio i.e. 0.00, 0.25, 0.50, 0.75, 1.00, 1.25, 1.50, and 2.00 without adding any surfactant or a structure-directing reagent. As produced GO:NPO nanosheets exhibited an improved photocatalytic activity due to the spatial seperation of charge carriers through interface, where photoinduced electrons transferred from NiPO4 to the GO sheets without charge-recombination. Out of the series, the system 1.00 GO:NPO NC show the optimum hydrogen production activity (15.37 μmol H2 h−1) towards water splitting under the visible light irradiation. The electronic environment of the nanocomposite GO-NiO6/NiO4-PO4 elucidated in the light of advance experimental analyses and theoretical DFT spin density calculations. Structural advanmcement of composites are well correlated with their hydrogen production activity.