Selective photocatalysis is a very promising direction to improve the activities of photocatalysts. Combining the technique of molecular imprinting (MIP) with heterogeneous photocatalysis can be an appealing approach to achieve our aim. Herein, using the MIP technique, the monoclinic MIP-BiVO₄ was successfully synthesized by the presence of rhodamine B (RhB) during the hydrothermal synthesis. The synthesized MIP-BiVO₄ possessed better adsorptive and photocatalytic activities than pristine BiVO₄. RhB added in the synthesis process worked as a template and served a crucial role in the formation of the MIP-BiVO₄ morphology. The photoelectrochemical analysis verified the superiority of MIP-BiVO₄ sample in the transfer and separation of the electron-hole pairs. Holes played the most crucial role in the degradation of the pollutants. The effective approach combining MIP technique in the synthesis of photocatalysts would provide some guidance to selective photocatalysis field for designing and synthesizing highly efficient photocatalysts.