Unusual intense infrared-to-ultraviolet upconversion luminescence was observed in YF3:Yb3+(20%)/Tm3+(1%) nanocrystals under 980 nm excitation. The intense ultraviolet emissions (1I6→3H6, 1I6→3F4, and 1D2→3H6) were affirmed arising from the excitation processes of five-photon and four-photon. In comparison with the bulk sample with the same chemical compositions, ultraviolet upconversion lumi-nescence of the nanocrystals was markedly enhanced. Spectral analysis indicated that the enhancement was attributed to the decrease of Judd-Ofelt parameter Ω2, which precluded the transition rate from 3F2 to 3F4, enhanced the energy transfer process and populated the 1D2 level: 3F2→3H6 (Tm3+): 3H4→1D2 (Tm3+).