The quenching of the red Pr3+ (1D2 → 3H4) luminescence in a single crystal of KY(WO4)2 doped with Pr3+ is investigated at room temperature under high hydrostatic pressure. The quenching is ascribed to a pressure-induced downshift of the Pr3+ → W6+ metal-to-metal charge transfer (or impurity trapped exciton) state. The concomitant decrease of the 1D2 → 3H4 emission lifetime is reproduced using a phenomenological model. The fitting allows the determination of the pressure-induced shrinkage of the Pr3+(Y3+)-W6+ distance in the crystal. The value is consistent with the quantity previously determined in CaWO4 by means of X-ray diffraction.