By doping appropriate lanthanide ions, LiYF4 as a host luminescent material can simultaneously exhibit bright visible-light emission. A series of LiYF4:Yb3+/Ho3+ microparticles with different Mg2+ doping concentrations were synthesized and investigated. The crystal structure of the synthesized microparticles was tested by X-ray diffraction (XRD). Notably, a significant increase in the upconversion photoluminescence intensity of upconversion microparticles (UCMPs) was obtained by introducing Mg2+ ions under 980 nm laser excitation, and achieved a maximum level when the concentration of Mg2+ ions was 8 mol%. Additionally, the practicality of the resultant UCMPs used as the raw material of anti-counterfeiting ink was systematically investigated. These results prove that the Mg2+-doped LiYF4:Yb3+/Ho3+ are very promising as screen-printing materials for anti-counterfeiting recognition labels.