High pressure studies of Cr2+ luminescence in ZnSe crystals were performed at low temperatures. Inaddition to the mid-infrared luminescence transitions from the first excited5E level, higher energy luminescence was also observed. These two luminescencebands exhibit similar pressure coefficients but of opposite signs, which identifythe origin of the higher energy band as the transitions from the second excited3T1 level. At higher pressures, increased covalence effects are observed, which result inthe appearance of an additional peak in the luminescence due to changes in the spin–orbit coupling strength.