Density Functional Theory and Time-Dependent Density Functional Theory calculations have been carried out on a recently synthesized amino-corrole and a corrole–azafullerene dyad which exhibits photoinduced electron transfer (PET). Good agreement of the theoretical results with experiment is obtained regarding the absorption and emission spectra of the corrole, the absorption spectra of the corrole–azafullerene dyad and the transient anionic and cationic radicals of azafullerene and corrole respectively. Application of Mulliken's theory for charge-transfer states yields the excitation energy of the charge-separated state of the dyad very close to the S1 excitation of amino-corrole, consistent with a PET process.