A two-step photodissociation mechanism was proposed in the literature for dinitrites in the absence of direct evidence of the intermediate species. In this work, photodissociation dynamics of cis and trans 1,3-cyclohexane dinitrites are investigated by laser-induced fluorescence (LIF) spectroscopy and theoretical calculation methods. Observation of the fluorescence spectra of the 3-nitrosooxy cyclohexoxy radical provides direct experimental evidence that the intermediate species exists. The results indicate that photodissociation of dinitrites indeed follows a two-step mechanism, i.e. one of the O–NO bonds of the molecule breaks first upon 355 nm laser photolysis and generates an alkoxy radical (RO) plus NO; the alkoxy radical further dissociates in the secondary dissociation step and produces small fragments such as vinoxy etc.