XeAuF has been detected and characterized using microwave rotational spectroscopy. It was prepared by laser ablation of Au in the presence of Xe and SF(6), 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 (131)Xe and (197)Au nuclear quadrupole coupling constants have been evaluated. The molecule is linear, with a short XeAu bond (2.54 A), 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 approximately 100 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.