The photocatalytic composites based on BiVO4, TiO2 nanotubes (TNT) and reduced graphene oxide (RGO) were synthesized by a one‐step hydrothermal synthesis method. The properties and structures of the samples were characterized by SEM, XRD, UV‐Vis DRS, Raman spectroscopy, photoluminescence spectroscopy and XPS. The effects of RGO‐TNT loading, pH, and dosage of catalysts on degradation efficiency were tested. The best removal results were occured on the condition that loading amount of RGO‐TNT was 10 %, solution pH 10, and catalyst dosage was 1.4 g L−1. The obtained ternary composite with 10 wt% RGO‐TNT exhibited a significant enhancement in photocatalytic efficiency due to the lower band gap with enhanced light absorption and a suppression in the recombination rates of the photogenerated charge carriers, and about 73 % of imidacloprid was degraded within 30 min under UV irradiation. Furthermore, BiVO4/RGO‐TNT‐10 can be reused for 6 times without obvious catalysis loss. Trapping experiments showed that hydroxyl radicals were the main active species in the imidacloprid photocatalytic degradation, and a possible photocatalytic mechanism was proposed based on the results of trapping experiments.