The mechanisms of the photochemical isomerization reactions were investigated theoretically using a model system of 2-cyanopyrrole and 2-cyano-5-methylpyrrole with the CASSCF (eight-electron/seven-orbital active space) and MP2-CAS methods and the 6-311(d,p) basis set. The structures of the conical intersections, which play a decisive role in such phototranspositions, were obtained. The intermediates and transition structures of the ground state were also calculated to assist in providing a qualitative explanation of the reaction pathways. Our model investigations suggest that the preferred reaction route for the cyanopyrroles is as follows: reactant -> Franck-Condon region -> conical intersection -> photoproduct. In particular, the conical intersection mechanism found in this work gives a better explanation than the previously proposed internal cyclization-isomerization mechanism and supports the experimental observations. In addition, we suggest a simple p-pi orbital topology model, which can be used as a guide tool to predict the location at which conical intersections are likely to occur, as well as the conformations of the phototransposition products of various heterocycles.