Recent studies have shown that the composite of semiconductor photocatalytic materials and g-C3N4 can effectively inhibit photocatalytic carrier recombination and enhance the adsorption performance of the composite photocatalytic materials, so that the composite photocatalyst has stronger photocatalytic activity. In this paper, three kinds of graphitic carbon nitride photocatalyst g-C3N4 with different morphologies were prepared using the same precursor system by the chemical cracking method. After characterization and application, the sample with the most significant photocatalytic activity was selected and the g-C3N4/BiVO4 heterostructure was synthesized by the simple solvent evaporation method, then the photocatalytic experiment was carried out. The results show that, when the content of BiVO4 in the composite sample is 1%, the photocatalytic activity of RhB was the highest, and the degradation rate could reach 90.4%. The kinetic results showed that the degradation of RhB was consistent with the quasi-primary degradation kinetic model. The results of the photocatalytic cycle experiment show that the photocatalytic performance remains unchanged and stable after four photocatalytic cycles. The existence of a g-C3N4/BiVO4 binary heterojunction was confirmed by UV/Visible diffuse reflection (UV-DRS) and photoluminescence (PL) experiments. Owing to the Z-type charge process between BiVO4 and g-C3N4, efficient carrier separation was achieved, thus enhancing the photocatalytic capacity. This work provides a new idea for the study of heterojunction photocatalytic materials based on g-C3N4.