BiVO4 is ubiquitously known for its potential use as photoanode for PEC-WS due to its well-suited band structure; nevertheless, it suffers from the major drawback of a slow electron hole separation and transportation. We have demonstrated the one-pot synthesis of BiVO4/Ag/rGO hybrid photoanodes on a fluorine-doped tin oxide (FTO)-coated glass substrate using a facile and cost-effective hydrothermal method. The structural, morphological, and optical properties were extensively examined, confirming the formation of hybrid heterostructures. Ternary BiVO4/Ag/rGO hybrid photoanode electrode showed enhanced PEC performance with photocurrent densities (J ph ) of ~2.25 and 5 mA/cm2 for the water and sulfate oxidation, respectively. In addition, the BiVO4/Ag/rGO hybrid photoanode can convert up to 3.5% of the illuminating light into photocurrent, and exhibits a 0.9% solar-to-hydrogen conversion efficiency. Similarly, the photocatalytic methylene blue (MB) degradation afforded the highest degradation rate constant value (k = 1.03 × 10-2 min-1) for the BiVO4/Ag/rGO hybrid sample. It is noteworthy that the PEC/photocatalytic performance of BiVO4/Ag/rGO hybrid architectures is markedly more significant than that of the pristine BiVO4 sample. The enhanced PEC/photocatalytic performance of the synthesized BiVO4/Ag/rGO hybrid sample can be attributed to the combined effects of strong visible light absorption, improved charge separation-transportation and excellent surface properties.