sEDA, pEDA, and cSAR descriptors of the substituent effect were determined for >30 monosubstituted benzenes in the first excited singlet S, state at the LC-omega B97XD/ aug-cc-pVTZ level. It was found that in the S, state, the sigma- and pi valence electrons are a bit less and a bit more affected, respectively, than in the S-0 state,( )but basically, the effect in both states remains the same. In the S-0 and S,( )states(1), the d(C-X) distances to the substituent's first'atom and the ring perimeter correlate with the sEDA and pEDA in the appropriate states, respectively. The energies and the gap of the frontier orbitals in the two states are linearly correlated and for the HOMO(S,), LUMO1S1), and (H)OMfXSj)-LUO(((1))) gap c(1)rrelate also with the pEDA<^>) and c(S(1)AR(S,) descr(1)ptors. In all studied correlations, three similar groups of substituents can be distinguished, for which correlations (i) are very good, (ii) deviate slightly, and (iii) deviate significantly. Comparison of the shape of the HOMO(S-0) and HOMO<^>) orbit(S(1)ls shows that for case (i) HOMO orbitals exhibit almost perfect antisymmetry against the benzene plane, for case (ii) the antisymmetry of HOMO in one of the states is either perturbed or changed, and for case (iii) one HOMO state has a- chara sigma ter.