Li ions affect the upconversion efficiency by changing the local crystal field of the luminescent center. Herein, in order to improve the upconversion efficiency of NaYF₄:Yb³⁺/Eu³⁺, a series of NaYF₄:Yb³⁺/Eu³⁺ micro-particles with different Li⁺ doping concentrations were synthesized by the hydrothermal synthesis method, respectively. Firstly, the structure and morphology of NaYF₄:Yb³⁺/Eu³⁺ upconversion micro-particles (UCMPs) with different doping concentrations were analyzed by X-ray diffraction and a scanning electron microscope (SEM). SEM results show that the UCMPs are not only highly crystallized, but also have hexagons with different Li⁺ concentrations of NaYF₄:Yb³⁺/Eu³⁺. X-ray diffraction shows that the crystal field around Eu³⁺ changes with the increase of Li⁺ concentration. Then, the fluorescence spectrum of NaYF₄:Yb³⁺/Eu³⁺ was studied under the irradiation of a 980 nm laser. The results show that the fluorescence intensity of NaYF₄:Yb³⁺/Eu³⁺ with 2% Li⁺ is the strongest, which is twice the intensity of NaYF₄:Yb³⁺/Eu³⁺ without Li⁺. Finally, the fluorescence imaging analysis of NaYF₄:Yb³⁺/Eu³⁺ with 2% Li⁺ concentration was carried out. The UCMPs are used to screen printing to evaluate the imaging effect on different sample surfaces. The results show NaYF₄:Yb³⁺/Eu³⁺ (with 2% Li⁺) has great application prospects in anti-counterfeiting recognition.