Herein, we report a class of unprecedented oxime ester-based bifunctional nitrogen-radical precursors to be utilized for the simultaneous generation of ambiphilic iminyl and electrophilic amidyl radicals via an energy transfer strategy, therefore providing a rapid and versatile protocol for unsymmetrical diamination of various electron-rich (hetero)arenes and alkenes. Noteworthy features of this method include: 1) this mild diamination reaction was performed with a cheap and commercially available thioxanthone as organic photosensitizer, without requirement of any transition-metals and additives, thus being of high practicability; 2) moreover, this protocol exhibits remarkable compatibility in dearomative diamination of a variety of (hetero)arenes, and is of exclusive diastereo-and regioselectivity, thanks to the different reactivities of iminyl and amidyl radicals; 3) most notably, the formed vicinal diamines bear two differentiated amino functionalities, and either imine or amide groups could be easily and orthogonally converted into unprotected amines, thereby facilitating the downstream transformation. Taken together, the current protocol offers a promising solution towards the main limitations of catalytic diamination.