By utilizing the XMS-CASPT2 method, insights into the molecular geometries and electronic structures of both the unsubstituted and meso-triphenyl copper corroles are provided. Both systems adopt a saddled geometry in their ground electronic state (S 0 ), characterized by a multiconfigurational electronic structure with three dominant configurations. This structural saddling arises due to electron transfer from a corrole π orbital to the d x 2 -y 2 orbital of the metal ion. Although the geometry optimizations were carried out with a minimal active space of (4e,5o), good agreement with available experimental data is obtained. Moreover, the choice of the active space was validated by performing an electronic structure study and comparing spin state energetics with larger complete and restricted active spaces. The resulting enthalpy differences are consistent with results from variable temperature NMR.