Photocatalytic CO2 reduction plays a crucial role in advancing solar fuels, and enhancing the efficiency of the chosen photocatalysts is essential for sustainable energy production. This study demonstrates advancements in the performance of g-C3N4 as a photocatalyst achieved through surface modifications such as exfoliation to increase surface area and surface oxidation for improved charge separation. We also introduce reduced graphene oxide (rGO) in various ratios to both bulk and exfoliated g-C3N4, which effectively mitigates charge recombination and establishes an optimal ratio for enhanced efficiency. g-C3N4/rGO serves to fabricate a hybrid organic/inorganic heterojunction with Cs3Bi2Br9, resulting in a g-C3N4/rGO/Cs3Bi2Br9 composite. This leads to a remarkable increase in photocatalytic conversion of CO2 and H2O to CO, H2 and CH4 at rates of 54.3 (±2.0) μmole− g−1 h−1, surpassing that of pure Cs3Bi2Br9 (11.2 ± 0.4 μmole− g−1 h−1) and bulk g-C3N4 (5.5 ± 0.5 μmole− g−1 h−1). The experimentally determined energy diagram indicates that rGO acts as a solid redox mediator between g-C3N4 and Cs3Bi2Br9 in a Z-scheme heterojunction configuration, ensuring that the semiconductor (Cs3Bi2Br9) with the shallowest conduction band drives the reduction and the one with the deepest valence band (g-C3N4) drives the oxidation. The successful formation of this high-performance heterojunction underscores the potential of the developed composite as a photocatalyst for CO2 reduction, offering promising prospects for advancing the field of solar fuels and achieving sustainable energy goals.