Ultraviolet fluorescence of Nd 3+ ions induced by triphotonic excitation process was studied in Nd-doped LiYF 4 , LiLuF 4 and BaY 2 F 8 crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f 2 5d configuration and 4f 3 states of Nd 3+ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of 4 K 11/2 (5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f 2 configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f–f characteristics to the f–d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262nm observed in LiYF 4 , LiLuF 4 and BaY 2 F 8 crystals, respectively. Although the 5d–4f 2 interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f 2 5d configuration to 4f 3 states that preserves the total spin S=3/2.