In this work, we fabricated NaYF4:Yb3+, Tm3+@NaYF4:Yb3+, Nd3+@TiO2 (Tm@Nd@TiO2) core@shell nanoparticles and investigated their near-infrared (NIR) photocatalytic activities. Comparing to traditional TiO2 based upconversion (UC) photocatalysts (i.e., NaYF4:Yb3+, Tm3+@TiO2, named Tm@TiO2), Tm@Nd@TiO2 exhibits enhanced photocatalytic activity under NIR light irradiation. The photocatalytic activity of Tm@Nd@TiO2 under 980, 808, and 980+ 808 nm laser irradiation is 4.40, 5.84, and 9.83 times as high as that of Tm@TiO2 under only 980 nm irradiation, respectively. The ethylene degradation rate of Tm@Nd@TiO2 under 980 + 808 nm laser irradiation is 6.4 times as that of Tm@TiO2. The photocatalytic activity of Tm@Nd@TiO2 under visible + NIR irradiation is even comparable with (similar to 2/3) that under UV light irradiation during Rhodamine B (RhB) degradation. The enhanced photocatalytic activity of Tm@Nd@TiO2 can be attributed to the stronger light absorption in NIR region ascribed to Nd3+, lower water absorption and the enhanced UC emission of Tm@Nd with unique core@shell nanostructures. This work can provide a possible route to improve the NIR photocatalytic activity and stimulate the applications in many other fields.