The nitrogen-decorated CeO2/reduced graphene oxide nanocomposite (CeO2/N-rGO) was one-step synthesized by a facile hydrothermal technique and applied as counter electrode materials for dye-sensitized solar cells (DSSCs). For comparison, CeO2/rGO and rGO were also synthesized by adjusting corresponding reactants. It was found that the as-synthesized CeO2/N-rGO shows better electrocatalytic activity for triiodide/iodide reduction than that of pure rGO and CeO2/rGO, and a synergistic effect of nitrogen and CeO2 on the rGO sheets was observed. The photoelectric conversion efficiency of DSSCs based on CeO2/N-rGO counter electrode was 3.20%, which is higher than that of CeO2/rGO (2.45%) and rGO counter electrode (1.37%). Furthermore, the synergistic effect of nitrogen and CeO2 on the rGO sheets was also discussed in detail with different CeO2 amount levels. It is believed that this one-step synthetic method is a potential way to synthesize low-cost and efficient rGO-based multiple composited counter electrode materials to replace more expensive Pt.