Kinetics and mechanism of the photoinduced reactions of 4-nitroveratrole (NV) with OH- and a number of aliphatic, amines have been studied by laser kinetic spectroscopy and by measurement of transient changes in electrical conductivity. In the case of OH- only reactions with NV in its lowest triplet state (T0) are observed and these lead to substitution of the OCH3 group at atom C(2) of the aromatic molecule and to formation of a number of transient σ-complexes, which return to NV. In the case of the amines both excited singlet state and triplet state reactions are observed. The singlet state reactions with methylamine and with n-hexylamine lead to substitution of the OCH3 group at atom C(2). Although piperidine quenches the excited singlet states involved, this does not lead to substitution at C(2). The triplet state reactions with the amines start with a discrete electron-transfer reaction in which the radical anion (E) of NV is formed. Subsequent reaction of E with the radical cation of the amine leads to substitution at C(l) and to a number of σ-complexes, which return to NV. © 1989, American Chemical Society. All rights reserved.