We have calculated α and η, the ionization and attachment coefficients, and (E/N) *, the limiting breakdown electric-field–to–gas-density ratio, in SF6 and SF6 mixtures by numerically solving the Boltzmann equation for the electron energy distribution. The calculations require a knowledge of several electron collision cross sections. Published momentum transfer and ionization cross sections for SF6 were used. We measured various attachment cross sections for SF6 using electron-beam techniques with mass spectrometric ion detection. We determined a total cross section for electronic excitation of SF6 by comparing the predicted values of α, η, and (E/N) * with our measured values obtained from spatial current growth experiments in SF6 in uniform fields over an extended range of E/N. With this self-consistent set of SF6 cross sections, together with published He and N2 cross sections, it was then possible to predict the dielectric properties of SF6-He and SF6-N2 mixtures. Published experimental values of α for the SF6-He mixtures lie between the values of α calculated with and without ionization of SF6 by excited He atoms. Published experimental values of (E/N) * agree with our calculations to within 5% in both the SF6-He and the SF6-N2 mixtures.