We report the application of plasmonic Bi nanoparticles supported rGO/BiVO4 anode for photoelectrochemical (PEC) water splitting. Nearly, 2.5 times higher activity was observed for Bi-rGO/BiVO4 composite than pristine BiVO4. Typical results indicated that Bi-rGO/BiVO4 exhibits the highest current density of 6.05 mA/cm2 at 1.23 V, whereas Bi–BiVO4 showed the current density of only 3.56 mA/cm2. This enhancement in PEC activity on introduction of Bi-rGO is due to the surface plasmonic behavior of BiNPs, which improves the absorption of radiation thereby reduces the charge recombination. Further, the composite electrode showed good solar to hydrogen conversion efficiency, appreciable incident photon-to-current efficiency and low charge transfer resistance. Hence, Bi-rGO/BiVO4 provides an opportunity to realize PEC water splitting. © 2019 Hydrogen Energy Publications LLC