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The schematic diagram display that graphene working as a bed on the surface of CN for gold nanoparticles and charge transport. Due to graphene this materials have very large surface area and efficiently high number active surface side. • Au-modified reduced graphene oxide (rGO) coupled graphitic carbon nitride. • Low-dimensional 0D/2D/2D photocatalytic system. • Water splitting and CO 2 conversion to energy dense molecules. • Two-step two-electron way of water oxidization through intermediate H 2 O 2 catalyzed by the adding rGO. Photocatalysis is regarded as one of promising technology for future clean and sustaniable energy applications. Herein, we have fabricated Au-modified reduced graphene oxide coupled with carbon nitride (Au/rGO/g-C 3 N 4) as novel 0D/2D/2D photocatalytic nanocomposites. The optimized sample 2Au/0.6rGO/g-C 3 N 4 exhibits exceptional visible-light activity for water splititng and CO 2 reduction with quantum efficiency of 3.82 % and 1.98 %, respectively. Electrochemistry and ultraviolent photoemission are combined to determine the band alignments and elaborate associated water splitting path-way mechanism. It is validated that due to intrinsic deep valence band position of g-C 3 N 4 , the obtained nanocomposites exhibit unusual two-step two-electron way of water oxidization through intermediate H 2 O 2 catalyzed by rGO addition. The exceptional photoactivities are attributed to dual functions of enhanced charge separation and two-electron water oxidization facilitated by rGO and surface plasmon effect of decorated Au. Our work provides illuminations for low cost and high efficiency photocatalytic water splitting and CO 2 reduction applications. [ABSTRACT FROM AUTHOR]