A photochemical dearomative vicinal aminooximation of heteroarenes with N-nitrosamines as bifunctional reagents is reported, enabling the synthesis of heterocyclic scaffolds with amino and oxime functionalities under mild catalyst-free conditions. A wide range of heteroarenes, including indoles and benzofurans, engaged in the reaction, and the bifunctionalized dearomatized products can further undergo diverse transformations to yield a variety of compounds.