Multireference configuration interaction (MRCI) calculations have been performed for pyrrole with the aim of providing an explanation for the experimentally observed photochemical deactivation processes. Potential energy curves and minima on the crossing seam were determined using the analytic MRCI gradient and nonadiabatic coupling features of the COLUMBUS program system. A new deactivation mechanism based on an out-of-plane ring deformation is presented. This mechanism directly couples the charge transfer π 1 π* and ground states. It may be responsible for more than 50% of the observed photofragments of π π* -excited pyrrole. The ring deformation mechanism should act complementary to the previously proposed NH-stretching mechanism, thus offering a more complete interpretation of the pyrrole photodynamics.