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 differ-ent 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.