C, N co-modified niobium pentoxide (Nb2O5) nanoneedles have been successfully synthesized via a facile hydrothermal method with Niobium Chloride (NbCl5) as a precursor and triethylamine as both the carbon and nitrogen source. The formation process of Nb2O5 nanoneedles has been presented in detail by investigating the effect of the crystallization temperature, the amount of triethylamine and the calcination temperature. The as-prepared Nb2O5 nanoneedles exhibit more efficient photocatalytic activity than commercial Degussa P25 and commercial Nb2O5 towards photodegradation of Rhodamine B (RhB) at a concentration of 10 mg L−1 under visible light. Special chemical species, such as carbonate species and NOX species, that exist on the surface of the as-prepared catalyst could extend the absorption into the visible region and thus enhance the photocatalytic activity of the Nb2O5 nanoneedles. At the same time, the obtained Nb2O5 nanoneedles exhibit excellent stability even after three successive cycles. A possible photodegradation mechanism was proposed and the corresponding photodecomposition process of RhB over the Nb2O5 nanoneedles was elucidated by a reactive species trapping experiment, suggesting that h+ and O2˙− play a major role in the photodegradation of RhB in aqueous solution.