XeAuF has been detected and characterized using microwave rotational spectroscopy. It was prepared by laser ablation of Au in the presence of Xe and SF6, and stabilized in a supersonic jet of Ar. The spectrum was measured with a cavity pulsed jet Fourier transform microwave spectrometer, in the frequency range 6-26 GHz. Rotational constants, centrifugal distortion constants, and Xe-131 and 197 Au nuclear quadrupole coupling constants have been evaluated. The molecule is linear, with a short XeAu bond (2.54 Angstrom), and is rigid. The 131 Xe nuclear quadrupole coupling constant (NQCC) is large (-135 MHz). The 197 Au NQCC differs radically from that of uncomplexed AuF. The results are supported by those of ab initio calculations which have given an XeAu dissociation energy similar to100 kj mol(-1), plus Mulliken and natural bond orbital populations, MOLDEN plots of valence orbitals, and an energy density distribution. All evidence is consistent with XeAu covalent bonding in XeAuF.