LiLuF₄ single crystals doped with Ce ³⁺ ion of 0.1mol% and Yb ³⁺ ion of concentration varying from 0 to 2.0mol% were successfully synthesized by an improved Bridgman method. Intense near-infrared emission at around 1020 nm, attributed to the ²F_5/2→ ²F_7/2 transition of Yb ³⁺, and ultraviolet emission of Ce ³⁺ at 300-350 nm (5d→4f) was observed using excitation at 291 nm. Influence of Yb ³⁺ ions concentration on the spectroscopic properties of Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystal and the mechanism of energy transfer from Ce ³⁺ to Yb ³⁺ ions were explored through optical absorption and emission spectra. The temperature dependent emission indicated that the emission intensity constantly decreases with the increase of temperature from 298 to 443 K due to the enhancement of non-radiative quenching at high temperature. Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystals mainly emit in the ultraviolet and near-infrared ranges. This unique property may be suitable for applications in anti-counterfeiting techniques and public security affairs.