Two triarylcorrole complexes, (hydroxy)[5,10,15-tritolylcorrolato]silicon-(TTC)Si(OH) and (dihydroxy)[5,10,15-tritolylcorrolato]phosphorous-(TTC)P(OH)2 , have been investigated by magnetic circular dichroism (MCD) and magnetic circularly polarized luminescence (MCPL). The spectroscopic investigations have been combined with explicit calculation of MCD response through time-dependent density functional theory (TD-DFT) formalism. This has allowed us to better define the role of molecular orbitals in the transitions associated with the Soret and Q bands. Besides and more importantly, MCD has made it possible to follow the titration process of (TTC)Si(OH) in dimethyl sulfoxide (DMSO) solution with NaF and of (TTC)P(OH)2 in dichloromethane solution with alcohols in a complementary and, we dare say, more sensitive way with respect to absorption and fluorescence data. Finally, the MCPL spectra and the ancillary TD-DFT calculations have allowed us to characterize the excited state of (TTC)Si(OH).