Owning to exceptional optical and physicochemical properties, lanthanide-doped inorganic dual-mode luminescence materials are regarded as promising platform for multifunctional applications. Herein, a facile hydrothermal method is used to integrate Ce³⁺ and Nd³⁺ ions co-doped NaLuF₄ phosphors, achieving dual-mode with ultraviolet (UV) and the second near-infrared (NIR-II) luminescence from single particles under two excitation sources. Higher NaF/LnCl₃ ratio can not only promote the crystal phase transformation from cubic to hexagonal and the shape evolution from nanoparticles to microprisms, but also promote the UV and NIR-II luminescence properties of NaLuF₄:Ce³⁺, Nd³⁺ phosphors. Upon irradiation with X-ray, Ce³⁺ and Nd³⁺ ions co-doped NaLuF₄ phosphors exhibit strong broad band UV emission due to 5d → 4f transition emission of Ce³⁺. Under 808 nm NIR excitation, the phosphors give NIR-II emission with two peaks at around 1060 nm and 1340 nm, which are attributed to the ⁴F_3/2 → ⁴I_11/2 and ⁴F_3/2 → ⁴I_13/2 electron transitions of Nd³⁺ ions respectively. Furthermore, the possible emission and energy transfer mechanism between Ce³⁺ and Nd³⁺ under the excitation of X-ray and 808 nm laser are discussed in details. The above results not only pave the way for future research of dual-mode luminescent materials, but also endow such materials with potential bio-applications for deep tissue bioimaging and therapy.