To improve the catalytic activity of Nb2O5, a composite Nb2O5/C (Nb2O5 imbedded in carbon support) is synthesized with a simple in situ method and then introduced the composite into dye-sensitized solar cells (DSCs) as a counter electrode (CE) catalyst. Based on the analysis of the cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel-polarization curve measurements, the catalytic activity of the Nb2O5/C composite for the regeneration of iodide-free redox couples of polysulfide (T-2/T-) and cobalt complex (Co3+/2+) is indeed enhanced significantly as compared with pure Nb2O5, because the composite electrode eliminates the particle aggregation and forms a mesoporous network structure with large pore size. The T-2/T- electrolyte based DSCs with Nb2O5/C CE yields a high power conversion efficiency (PCE) of 6.11%, generating a great improvement of 63.8% as compared to the Pt CE based DSCs. In addition, the Nb2O5/C exhibits higher catalytic activity than Pt for regenerating the Co3+/2+ redox couple and the DSCs using Nb2O5/C CE shows a high PCE of 9.86%. (C) 2016 Elsevier B.V. All rights reserved.