Rate constants for transfer between XeF(III,1/2) and XeF(II,3/2) states and quenching of XeF(III,1/2) have been measured using a method which employs the steady‐state photolysis of XeF2. For He, Ne, Ar, Kr, N2, CF4, and SF6transfer dominates over quenching; for Xe, NF3, CF3Cl, and CF3H quenching and transfer are competitive. Only for F2is quenching dominant. Based upon the relative emission intensities from XeF(III,1/2) and XeF(II,3/2) at high pressures of buffer gases, XeF(II,3/2) must be 0.08 eV lower in energy than XeF(III,1/2).