Using vanadium oxide (V2O5) inverse opal (IO) as a three-dimensional (3D) electron transporting tunnel, bismuth vanadate (BiVO4) as a light harvester, and Amorphous Nickel Hydroxide (NiOOH) as an oxygen evolution co-catalyst, a V2O5@BiVO4@NiOOH IO architecture was fabricated as an efficient photoanode on a conductive fluorine doped tin oxide (FTO) substrate for photoelectrochemical (PEC) water oxidation. V2O5 is the visible light absorbing photoanodes for water oxidation; however, the efficiency of this compound re- mains low (similar to 0.08 mA/cm(2) at 1.23 V vs. reversible hydrogen electrode (V-RNE)) and the un-favorable surface trap states limits the activity of V2O5 photoelectrodes in a PEC system. We found that the photoactive thin conductive BiVO4 (similar to 12 nm) in the V2O5 IO greatly enhanced the charge separation efficiency to achieve better PEC water oxidation through modification of the surface states. The subsequent addition of NiOOH as an effective Oxygen evolution catalyst subsequently reduces the large overpotential and generates the photocurrent density of 1.14 mA/cm(2) at 1.23 V-RHE. Electrochemical impedance spectros- copy (EIS) evidenced that NiOOH deposition can substantially lower the charge transfer resistance (R-CT) at the semiconductor interface. Specifically, the consecutive and ordered morphology renders direct conduction pathways for the extraction of photogenerated electron/hole pairs and the convenient structure to penetrate the photogenerated carriers toward the semiconductor surface over the electrolyte. It is expected that the uninterrupted pathways will improve the electron transportation and thus the charge collection properties. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.