The invention relates to a near-infrared long afterglow luminescent material and a preparation method thereof. The chemical composition expression of the material is Na 0.5 Ln 0.5 Ti 1‑x O 3 :xCr 3+ , where 0.001%≤x≤0.03%, and Ln selects Gd, La or Y. The content of Cr in this doping range can significantly enhance the afterglow intensity of the material, the luminescence wavelength of the material is in the range of 650-1050nm, the main peak is around 760nm, which is within the biological transparency window, and has good biological tissue penetration; The material can be effectively activated by deep red light and near-infrared light of 650-850 nm, and the reactivation of in vivo markers by external light source can be conveniently realized at any time. In addition, when the rare earth element Gd is selected, the long afterglow property can be quickly activated under the excitation of low-power low-energy light, and the material provided by the present invention has a high initial near-infrared afterglow intensity, high work efficiency, and high imaging sensitivity. At the same time, the material has good paramagnetic properties and can be used as a marker for magnetic resonance imaging to realize optical / magnetic resonance dual-function biological imaging.