The photochromic behavior of 2-(2',4'-dinitrobenzyl)pyridine (alpha-DNBP) has been followed in poly(methyl methacrylate) (PMMA) films and benzene solutions to clarify the behavior of a precursor state, previously identified in studies on crystalline alpha-DNBP at low temperatures. In PMMA films, photolysis at temperatures less than or equal to 50 K led to the concurrent formation of a NH tautomer and a colorless intermediate, which was stable for several hours. On irradiation at low temperatures and warming the sample, the colorless intermediate was seen to react to produce the NH tautomer in a higher yield than that found in the direct photolysis. Further information on this intermediate has come from flash photolysis studies in benzene solution, in which a new transient absorption has been observed at 335 nm and assigned to this species. This decays within a few microseconds at room temperature to form an OH tautomer, which then interconverts to the NH tautomer. The precursor state is not quenched by oxygen or naphthalene. From consideration of the kinetic and spectral data, it is suggested that this new species corresponds to a nonrelaxed tautomeric form of the OH state of alpha-DNBP.