Photoelectrochemical (PEC) energy conversion systems have been considered as a highly potential strategy for clean solar fuel production, simultaneously addressing the energy and environment challenges we are facing. Tremendous research efforts have been made to design and develop feasible unassisted PEC systems that can efficiently split water into hydrogen (H 2) and oxygen with only the energy input of sunlight. A fundamental understanding of the concepts involved in PEC water splitting and energy conversion efficiency enhancement for solar fuel production is important for better system design. This review gives a concise overview of the unassisted PEC devices with some state-of-the-art progress toward efficient PEC devices for future sustainable solar energy utilization.