XeCu covalent bonding has been found in the complexes XeCuF and XeCuCl. The molecules were characterized by Fourier transform microwave spectroscopy, supported by MP2 ab initio calculations. The complexes were prepared by laser ablation of Cu in the presence of Xe and SF(6) or Cl(2) and stabilized in supersonic jets of Ar. The rotational constants and centrifugal distortion constants show the XeCu bonds to be short and rigid. The (131)Xe, Cu, and Cl nuclear quadrupole coupling constants indicate major redistributions of the electron densities of Xe and CuF or CuCl on complex formation which cannot be accounted for by simple electrostatic effects. The MP2 calculations corroborate the XeCu bond lengths and predict XeCu dissociation energies approximately 50-60 kJ mol(-)(1). The latter cannot be accounted for in terms of induction energies. The MP2 calculations also predict valence molecular orbitals with significant shared electron density between Xe and Cu and negative local energy densities at the XeCu bond critical points. All evidence is consistent with XeCu covalent bonding.