Photoelectrochemical (PEC) conversion of solar energy into chemical energy urgently requires attractive photoelectrodes to advance its practical application. Herein, we demonstrated a simple dopant electron strategy for phase control engineering and prepared a hybrid photoelectrode of 1 T-MoS2 nanosheets sensitized monoclinic BiVO4 (denoted as 1 T-MoS2@BiVO4) with p–n junction. The internal p–n heterojunction in the composite photoanode contributes to its superior charges transport. Further, the inserted 1 T-MoS2 layer at the BiVO4/traditional co-catalysts (OECs) (OECs: FeOOH and NiOOH) interface can profoundly improve the PEC water splitting and solar conversion efficiency of BiVO4-based photoanodes. The corresponding photocurrent density of FeOOH@1T-MoS2@BiVO4 photoelectrode (4.02 mA cm−2) is 3.5 times as high as that of the pure BiVO4 electrode (1.14 mA cm−2) at 1.23 V vs reversible hydrogen electrode (RHE), accompanied by a photoconversion efficiency of 1.28% at 0.68 vs RHE. Theoretical integrated with experimental studies reveal that the insertion of an 1 T-MoS2 layer between BiVO4 and OECs facilitates the establishment of high speed transport channels for holes and electrons. Subsequently, copper phthalocyanine (CuPc) as an unconventional hole-transporting organic material could maintain the photocurrent density of the composite photoanode for stability test over 8 h. Importantly, this study sheds light on the rational design of phase-control-based devices for solar-to-chemical energy conversion, and also implies a prospective nexus between BiVO4 and traditional or unconventional co-catalysts.