Recently, studies on the luminescence properties of stable carbon-centered radicals have attracted great attention. Generally, they exhibit unusual photophysical properties such as long-wavelength emission, and high electro-luminescence quantum efficiency. However, most free radicals are shortlived because they are incredibly reactive due to the presence of unpaired electrons. In addition, most free radicals usually exhibit weak or no luminescence under ambient conditions and have long been used as quenchers of luminophores. Thus, the number organic luminescent radical species that persist under ambient conditions remains limited. Only a few free radicals that can stably luminesce at room temperature, e.g., triarylmethyl radical derivatives and N-heterocyclic carbene-based radicals have been reported so far. However, the design, synthesis, and purification of these radicals is relatively complicated given their high reactivity. This complexity has so far hampered progress in the design and development of fluorescent radicals. Hence, developing new strategies to generate and analyze fluorescent radicals remains highly desirable.