The Z-scheme Se/BiVO4 photocatalysts were successfully prepared by chemical reduction and hydrothermal methods. Ethanol had the effect of solubilizing a-Se and insoluble t-Se during aging, which was critical for the rapid growth of t-Se rods. Compared with pure Se rods and BiVO4, the Z-scheme Se/BiVO4 exhibits enhanced photocatalytic activity for rhodamine B (RhB) degradation under visible-light irradiation. The photoluminescence detection technology of terephthalic acid spectra shows that OH is the major active radical in the degradation of RhB by Se/BiVO4. Based on the transient photocurrent measurements and band structures, it can be concluded that the Z-scheme structure of Se/BiVO4 not only enhances the photogenerated electrons and holes migration rates but also to provide higher redox ability. With the enhanced photocatalytic performance, Se/BiVO4 can be potentially applied for the environmental remediation.