We report the upconversion luminescence of lithium fluoride single crystals excited by an infrared femtosecond laser at room temperature. The luminescence spectra demonstrate that upconversion luminescence originates from the color center of F3+. The dependence of fluorescence intensity on pump power reveals that a two-photon excitation process dominates the conversion of infrared radiation into visible emission. Simultaneous absorption of two infrared photons is suggested to produce the F3+ center population, which leads to the characteristic visible emission. The results are on the reveal and evaluation of the simultaneous two-photon absorption on the green upconversion process.