Aromatic compounds are one of the most abundant feedstocks in chemical industry, which typically focuses on their functionalization or full reduction. Partial reduction through dearomative sequences has been considerably less explored but would uncover the true potential of aromatic compounds in providing rapid access to complex and higher-value three-dimensional scaffolds. Several dearomative strategies have been established; however, most of these methods either necessitate metal-mediated multistep manipulations or are highly limited in their scope. Herein, an alternative photocatalytic radical cascade approach is disclosed, which exploits dearomative difunctionalization through selective dearomative spirocyclization/imination of nonactivated arenes. Various bifunctional oxime esters and carbonates are utilized in single-step installation of a range of functional groups concomitant with formation of a spiro-center and introduction of an iminyl functionality to furnish dearomatized spiro-imine scaffolds through tandem N–O bond cleavage, hydrogen-atom transfer, radical addition, 5-exo-trig cyclization, and radical cross-coupling sequences. The disclosed methodology allows formation of three or four new chemical bonds, including C−O, C−C, C−N bonds, in a single synthetic step, affording highly decorated three-dimensional structures from readily available starting materials.