Ar/Xe/NF3mixtures were excited by the focused beam from an ArF (193 nm) laser. Xe+ions are produced by two‐photon ionization, the electrons attach to make F−, and the ions recombine to make XeF*. Radiation is observed in the XeF(B 1/2) →XeF(X1/2) bands near 351 nm and in the broader XeF(C3/2) →XeF(A3/2) band near 460 nm. At low background gas pressure, mostlyB‐Xuv emission is observed. As the argon pressure is increased to 1000 Torr, the visible/uv band intensity ratio increases to about 3 to 1. We conclude from these results that theC(3/2) state lies 700±70 cm−1below theB(1/2) state. This conclusion should have a significant impact on our understanding of the fluorescence yields and laser performance of e‐beam‐excited XeF.