CeO2/Bi2MoO6 heterostructured microspheres were successfully synthesized through precipitation and hydrothermal method. The as-obtained samples were well characterized by XRD, SEM, TEM, UV–Vis DRS and XPS. The photocatalytic activity was evaluated by degrading acid orange II (AO-II) under visible light irradiation. The test results show that CeO2/Bi2MoO6 heterostructured microspheres have broad absorption in the visible region and have more superior catalytic activities than pure Bi2MoO6, which is attributed to the synergistic effect of the suitable band gap matching between CeO2 and Bi2MoO6. Moreover, 0.1CeO2/Bi2MoO6 composite has the highest activity. Radical scavenger experiments proves that the superoxide radical anions (O2−) and photogenerated holes (h+) are dominating active species. The recycling experiment confirms that CeO2/Bi2MoO6 heterostructure keep high stabilization during the photocatalytic reaction. On this basis, a photogenerated charge carriers transfer and photocatalytic progress on the CeO2/Bi2MoO6 heterostructure has been discussed.