Site‐selective spectroscopy reveals that Nd3+ions occupy more than 40 different crystal‐field environments in Sr5(VO4)3F. Preferential energy transfer to the site responsible for 1 &mgr;m lasing occurs but becomes less complete with increasing temperature. The4Iand4F3/2Stark levels of the lasing site have been determined and an analysis of the crystal field performed. From the crystal‐field fitting parametersBkq, a calculated energy‐level spectrum is determined up to 17 500 cm−1with a rms deviation from the available experimental levels of 6 cm−1. ©1995 American Institute of Physics.