FTO inverse opals (IOs) having a pore size of approximately 300 nm in the 400 nm sized polystyrene bead (PS) templates were developed by a spin-coating-assisted sol-gel process. Upon this template, the FTO/WO₃ core-shell IOs were developed by the facile electrodeposition under a constant potential (-0.5 VAg/AgCl(sat.)). Furthermore, upon the FTO/WO₃ core-shell IOs, BiVO₄ shell layers were covered by electrodeposition under a constant current (2 mA/cm2). The optimum photoelectrochemical (PEC) response was achieved with Co-Pi catalyst (FTO/WO3/BiVO4/Co-Pi), which exhibited the highest photocurrent density (Jsc) more than 5 mA/cm2 (1.23 VRHE) under full-sun conditions. In conclusion, considering that the favorable cascading band alignment can boost the fast charge separation and transport through the conductive FTO IO skeleton. Herein, the PEC performance and other results would be presented.