Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for XeF(+), XeF(-), XeF(2), XeF(4), XeF(5)(-), and XeF(6) from coupled cluster theory (CCSD(T)) calculations with new correlation-consistent basis sets for Xe. To achieve near chemical accuracy (+/-1 kcal/mol), up to four corrections were added to the complete basis set binding energies based on frozen core coupled cluster theory energies: a correction for core-valence effects, a correction for scalar relativistic effects, a correction for first-order atomic spin-orbit effects, and in some cases, a second-order spin-orbit correction. Vibrational zero-point energies were computed at the coupled cluster level of theory. The structure of XeF(6) is difficult to obtain with the C(3)(v)() and O(h)() structures having essentially the same energy. The O(h)() structure is only 0.19 kcal/mol below the C(3)(v)() one at the CCSD(T)/CBS level using an approximate geometry for the C(3)(v)() structure. With an optimized C(3)(v)() geometry, the C(3)(v)() structure would probably become slightly lower in energy than the O(h)() one. The calculated heats of formation for the neutral XeF(n)() fluorides are less negative than the experimental values from the equilibrium measurements by 2.0, 7.7, and 12.2 kcal/mol for n = 2, 4, and 6, respectively. For the experimental values, derived from the photoionization measurements, this discrepancy becomes even larger, suggesting a need for a redetermination of the experimental values. Evidence is presented for the fluxionality of XeF(6) caused by the presence of a sterically active, free valence electron pair on Xe.