The well-known stability of rylene diimides with varying nvalues (ranging from 0 to 7, where n=1 for naphthalenediimide or NDI), for generating stable radical-anions and thus finding diverse applications in organic materials, including self-healing and selfresponsive materials prompted us to explore the framework for design our photoswitchable radical system. We have successfully produced a durable NDI-based radical that remained active for more than a month in an aqueous environment by attaching NDI-cores to histidinyl units, serving as photo-induced electron donors. Based on earlier studies that demonstrated light-controlled electron transfer for generating charge-separated dipoles, we also recognized the effectiveness of a dimethyldihydropyrene (DHP) switch as an electron donor in the closed state, while in the open cyclophaendiene form it is less conjugated, and hence is not a good donor. The negatively photochromic DHP exhibits a planar, highly aromatic character in its closed form. Upon exposure to visible light, the closed isomer converts into the nonplanar, less aromatic open cyclophanediene (CPD) form, which can revert to DHP under UV exposure or thermal heating. Our research group recently reported a stable di-radical system within a conjugated DHP framework. Consequently, we envisioned that by integrating a photochromic DHP system into the NDI structure, specifically through DHP-NDI-DHP connectivity, where the electron-donation from the DHP form could produce an NDI-based radical-anion. The photoisomerized CPD unit, having a poor-donor ability, cannot generate the radical species in the CPD-NDI-CPD form. Thus, this system could demonstrate a reversible generation and destruction of an organic radical species through light-induced switching. This is indeed what was observed. The radical is highly fluorescing whereas the open-form which is diamagnetic has a low emission. Thus, the electron paramagnetic resonance (EPR) and emission signals provide dual orthogonal modes for the read-out of the system.