The luminescence behavior of 1% V3+:Cs2NaYCl6 at room temperature is studied as a function of hydrostatic pressure. At ambient pressure the V3+ (3)T(2)g excited state origin lies 234 cm(-1) above the T-1(2g) first excited state. At room temperature the two states are in thermal equilibrium, and spin-allowed T-1(2g) --> T-1(1g) emission is dominant. Pressure increases the energetic separation of T-1(2g) and T-1(2g), leading to a decreasing IT,, steady state population at constant temperature. This manifests itself in an increasing relative amount of spin-forbidden T-1(2g) --> T-1(2g) luminescence, as evidenced by the occurrence of sharp luminescence features and an increase in the luminescence decay time at higher pressures. (C) 2002 Published by Elsevier Science B.V.