The effects of spin-orbit coupling and other relativistic interactions on the electronic structure of the arsenic fluoride molecule are analyzed with the aid of ab initio configuration interaction calculations based on effective core potentials. The computed results for potential curves. vibrational wavefunctions and radiative transition probabilities between various low-lying states of AsF are compared with analogous data for the fluorides of the heavier Group V, atoms, antimony and bismuth. Measured spinorbit splittings for the X 'Z-and A 'Il h-s states are accurately reproduced in the relativtstic Cl and computed trends in the parallel and perpendicular bO+-X transition probabilities for this group of fluorides are found to agree with the observations of Cohn, Herman and Prevot. Inclusion of a semidiffuse s orbital on the fluorine atom is important in describing the 8 MO occupied in the A 'Il and c 'HI-s states. Computed electric dipole moments indicate that the latter states are more strongly polarized (negative F) than their lower-energy counterparts with & electronic configurations.