The luminescence behavior of 1% V 3 + :Cs 2 NaYCl 6 at room temperature is studied as a function of hydrostatic pressure. At ambient pressure the V 3 + 3 T 2 g excited state origin lies 234cm - 1 above the 1 T 2 g first excited state. At room temperature the two states are in thermal equilibrium, and spin-allowed 3 T 2 g -> 3 T 1 g emission is dominant. Pressure increases the energetic separation of 1 T 2 g and 3 T 2 g , leading to a decreasing 3 T 2 g steady state population at constant temperature. This manifests itself in an increasing relative amount of spin-forbidden 1 T 2 g -> 3 T 2 g luminescence, as evidenced by the occurrence of sharp luminescence features and an increase in the luminescence decay time at higher pressures.