sEDA, pEDA, and cSAR descriptors of the substituent effect were determined for >30 monosubstituted benzenes in the first excited singlet S1 state at the LC-ωB97XD/aug-cc-pVTZ level. It was found that in the S1 state, the σ- and π-valence electrons are a bit less and a bit more affected, respectively, than in the S0 state, but basically, the effect in both states remains the same. In the S0 and S1 states, 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(S1), LUMO(S1), and HOMO(S1)-LUMO(S1) gap correlate also with the pEDA(S1) and cSAR(S1) descriptors. 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(S0) and HOMO(S1) orbitals 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 σ-character.