Femtosecond transient absorption experiments and density functional calculations are presented for 2-methyl-1-nitronaphthalene, 2-nitronaphthalene, and 1-nitronaphthalene in cyclohexane and acetonitrile solutions. Excitation of 2-methyl-1-nitronaphthalene at 340 nm populates the Franck-Condon singlet state, which bifurcates into two barrierless decay channels with sub-200-fs lifetimes. The primary decay channel connects the Franck-Condon singlet excited state with a receiver triplet state, whereas the second, minor channel involves conformational relaxation to populate an intramolecular charge-transfer state, as previously reported for 1-nitronaphthalene (J. Chem. Phys. 2009, 113, 224518). Conversely, the experimental and computational data for 2-nitronaphthalene shows that almost the entire Franck-Condon singlet excited-state population intersystem crosses to the triplet state in less than 200 fs due to a sizable energy barrier of ca. 5 kcal/mol that must be surmounted to access the intramolecular charge-transfer state. Our results lend support to the idea that the probability of population transfer to the triplet manifold in these nitronaphthalene derivatives is controlled not only by the small energy gap between the Franck-Condon singlet excited state and the receiver triplet state but also by the region of configuration space sampled in the singlet excited-state potential energy surface at the time of excitation. It is proposed that the ultrafast intersystem crossing dynamics in these nitronaphthalene molecules most likely occurs between nonequilibrated excited states in the strongly nonadiabatic regime.