In this study, a novel photocatalyst composed of N-doped TiO 2 (N-TiO 2 ) and (Ca, Y)F 2 :Yb 3+ , Tm 3+ was prepared by simple dealloying followed by a hydrothermal method. The composite exhibits a homogeneous nanoporous structure consisting of large quantities of the spindle-like N-doped TiO 2 nanorods, on which the (Ca, Y)F 2 :Yb 3+ , Tm 3+ particles with a diameter of around 5 nm are uniformly dispersed. In addition, morphology and property of the N-TiO 2 can be controlled by adjusting the dealloying period. Results show that a short immersion time leads to a small size, large surface area and low band gap. As a result, the N-TiO 2 / (Ca, Y)F 2 :Yb 3+ , Tm 3+ composite after dealloying for 48 h (TiO 2 -48-C) exhibits higher degradation rates (65.6% for 10 h irradiation by 980 nm NIR) than others after dealloying for 60 h (TiO 2 -60-C) and 72 h (TiO 2 -72-C), indicating its excellent potential for practical applications.