The lowest excited triplet state of free-base 5,10,15-trispentafluorophenylcorrole (H(3)Cor) was studied in rigid glass by time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. Triplet sublevels were experimentally determined by using magnetophotoselection and liquid crystal. Quantum chemical calculations of zero-field splitting parameters D and E were used for the sublevel assignment. The out-of-plane sublevel T(z) was found to be the lowest; namely, D is positive for H(3)Cor, in contrast to previous reports. The origin of the difference is discussed in detail. Preliminary TR-EPR experiments on rhodium corrole, accompanied by the quantum chemical calculations, emphasize the important contribution of spin-orbit couplings. (C) 2011 Elsevier B. V. All rights reserved.