Solid-state as well as solution-state photochemistry of the donor-acceptor complexes derived from an aromatic amine and an aromatic nitro compound was investigated. Of the twelve adduct crystals studied, only three involving m-DNB as the acceptor (9-MC/m-DNB, 9-EC/m-DNB and DMAP/m-DNB) were found to be photoreactive in the solid state, producing photoredox products probably through hydrogen abstraction by the excited nitro group. The FT-IR study has implicated that the NO2 group of m-DNB may be interacting with the donor's amino group in the crystalline state.