The nature of the lowest energy triplet state (T1) of p-nitroaniline (PNA), N,N-dimethyl-p-nitroaniline (DMPNA) and nitrobenzene (NB) is reexamd. using the semiempirical CNDO/S-CI method with selected parameter options. In the case of the unperturbed mols. the short-axis polarized p* <- n(p) triplet largely localized at the acceptor end of the mol. may lie lower in energy than the triplet manifold counterpart of the intense intramol. charge-transfer D+ -> A- singlet excitation. Computations suggest, however, that polar solvents strongly stabilize the PNA and DMPNA p* <- p charge-transfer triplet relative to other excitations, whereas specific solvent hydrogen-bonded interactions stabilize the p* <- n(s) triplet of NB below those of p* <- p character. These assignments allow a rationalization of phosphorescence lifetime data, Tn <- T1 absorption measurements and relative photochem. behavior.