An efficient method for visible-light-triggered generation of radicals from mono- and dinitro-substituted perylenediimide derivatives is developed. UV-vis-NIR and electron paramagnetic resonance measurements were carried out to confirm the formation of radicals. Most importantly, these radical anions were remarkably stable for several months. Subsequently, the reversible nature of anions was validated by both chemical and spectroelectrochemical methods for applications in electrochromic materials.