Using fast beam photofragment spectroscopy, we have studied the competition between photodissociation and photodetachment in O2−. The photodissociation fraction is ∼10% and increases somewhat between 285 and 266 nm. High resolution photofragment spectroscopy shows that the O2− beam is composed of v = 0 ions only. The photofragment angular distribution has an anisotropy parameter β=1.9, indicating that the process of dissociation has a parallel character, attributed to the A 2Πu←X 2Πg transition. A detailed analysis of the kinetic energy release of the photofragments shows the structure related to the distribution over the six fine-structure dissociation limits O− (2P3/2,1/2)+O (3P2,1,0). The results are compared with an analytical diabatic dissociation model, taking into account the long range charge–quadrupole interactions; the A 2Πu is described in a Born–Oppenheimer electrostatic aproximation and projected onto the different fine-structure states at large internuclear separation using analytical expressions derived from the long range charge–quadrupole interactions between O− and O fragments. © 2003 American Institute of Physics.