We studied the ion-pair formation dynamics of F-2 at 18.385 eV (67.439 nm) using the velocity map imaging method. It was found that there are two dissociation channels corresponding to production of F+(1132) + F-(1 SO) and F+((3)Pj) + F-(1 SO). The measured center-of-mass translational energy distribution shows that about 98% of the dissociation occurs via the F+(D-1(2)) Channel. The measured angular distributions of the photofragments indicate that dissociation for the F+((3)Pj) channel occurs via predissociation of Rydberg states converging to F-2(+) (A(2) IIu) and dissociation for the F+(D-1(2),) channel involves mainly a direct perpendicular transition into the ion-pair state, or X-1 Sigma(g) -> 2(1)II(u), which is also supported by the transition dipole moment calculations.