Photoelectrochemical for energy production and storage from graphene-based metal oxide frame works have attracted an increasing attention in today research era. Particularly in tuning the surface area, electron transferability, functionality, and stability of graphene-based metal oxide, composites have opened wide scope for the photoelectrochemical applications. A plausible mechanism for the formation of graphene-based metal oxide composites improved photoelectrochemical performance due to their growth orientations, and physiochemical properties are given in detail. The enhanced efficiency is being entrenched in suppressed charge carrier recombination, which leads to better harvesting of photo-electron charge carriers. The assembly of metal oxide on graphene framework stands as a potential applicant for photoelectrochemical energy production (water splitting). This book chapter highlights on synthesis of graphene-based metal oxide composites framework and recent trends of their application as electrode materials toward photoelectrochemical water splitting.