In the present work, we have introduced a series of stable radical-doped coordination compounds composed of donor-acceptor structures and shown to produce organic radicals in situ as a result of unconventional lone pair-π interactions in ambient conditions. Inconspicuous lone pair-π and C-Hπ interactions were shown to play a key role in self-assembly as well as the charge transfer process, resulting in a long-lived charge-separated state able to generate organic radicals. The resultant species displayed broad-spectrum antimicrobial activity, including against multi-drug-resistant bacteria. This study unveiled the promise of reactive organic radical-doped materials as a new platform for developing antimicrobial agents that can overcome antibiotic resistance.