Self‐consistent Dirac–Slater multiple scattering calculations are presented for UF6. These are the first such calculations to be reported, and the results are compared critically to other relativistic calculations. The results of all molecular orbital calculations are in good qualitative agreement, as measured by energy levels, population analyses, and spin–orbit splittings. The overall charge distribution is computed to be U+1.5(F−0.25)6. Polarization functions are found to be qualitatively unimportant. A detailed comparison is made to the relativistic Xα (RXα) method of Wood and Boring, which also uses multiple scattering theory, but incorporates relativistic effects in a more approximate fashion. For the most part, the RXα results are in excellent agreement with the present results. Some differences of possible significance are noted in the lower valence and core energies.