The photophysics of most nitrated polycyclic aromatic compounds is dominated by an ultrafast intersystem crossing channel, which makes their first singlet excited states decay with rates on the order of 10(12) to 10(13) Some questions, however, remain about the nature of the receiver triplet states, which have been in principle assigned to specific triplets of a different electronic configuration from T-1. In particular, it could be suggested that even a small degree of n-pi* character of the T-1 state may be enough to allow the S-1 state to couple to upper vibronic states of the lowest energy triplet, without the requirement for specific upper triplet states. In this report, we show that there are, in fact, nitroaromatic compounds that do not show the ultrafast intersystem crossing channel but instead have S-1 states that are two to three orders of magnitude longer lived. Our studies focused on the time resolution of the emission from singly nitrated pyrenes, which show a strong photophysical dependence on the position of the NO2 group: Whereas S-1 in 1-nitropyrene is short-lived (up to 3 ps), in 4-nitropyrene and 2-nitropyrene this state has 0.41 and 1.2 ns lifetimes, respectively, in acetonitrile solution. Computational work at the TD-DFT level of theory indicates that such remarkable increase in the first excited singlet lifetime can indeed be explained by a loss of the energy coincidence between the Si state with specific upper triplet states formed from transitions that involve the nonbonding orbitals at the oxygen atoms. These results are in strong support of the previous descriptions about the requirement for intermediacy of specific triplet states in the ultrafast decay of the fluorescent state present in most nitroaromatics. The implications for the photochemistry of this group of toxic atmospheric pollutants, including the channel that redounds in the dissociation of the NO center dot fragment, are discussed in view of the present results.