Abstract Previously, a relatively large splitting of the 2E g state of Cr 3+ in grossular Ca 3Al 2[SiO 4] 3 has been reported [M. Czaja and Z. Mazurak, Opt. Mater 3 (1994) 95]. The absorption and luminescence spectra of crystals containing Cr 3+ and V 3+in grossular Ca 3Al 2(SiO 4) 3 garnets (variety tsavorite) have been studied for the first time. From these spectra measured at room and liquid helium temperatures we determined energies of R 2, R 1, and 4T 2g levels of Cr 3+. The lifetimes and splitting of the 2E g state have been measured by tuning the excitation energy within the inhomogeneous profile of the R 1 and R 2 lines of the split 2E g → 4A 2g transition. To account for the thermal quenching of the R-lines, it is necessary to recognize that the two components of the doublet may have remarkably different radiative lifetimes (7500 and 2500 μs). These lifetimes were obtained from low temperature decay and from the temperature dependence of the intensity ratio of the R 2, R 1 components. These separate lifetimes as well as the lifetime of the 4T 2g state were then set to fit the temperature dependence of the joint effective lifetime. The optical fluorescence of a V 3+ dopant is characterized by the broad band infrared fluorescence spectrum associated with short decay time < 1μs.