Poly-substituted quinolines represent an important structural motif in numerous biologically active products. Their preparation methods usually have disadvantages including expensive and dangerous materials, non-green solvents, multi-step process, and high temperature. Therefore, an efficient, green synthetic protocol for the design of multiply substituted quinoline derivatives with a wide variety of appended functional groups has tremendous practical significance. In this study, we provide a myriad of examples of photo-catalytically generated imine radicals that can undergo intramolecular electrophilic and nucleophilic addition reactions in the presence of organic and inorganic bases, respectively, to produce various poly-substituted quinoline derivatives. The highatom economy, good yields, mild reaction condition, simple experimental setup of this methodology, will prompted the development of new protocols for other heterocycles synthesis via using intramolecular Michael addition and anti-Michael addition of free radicals. Moreover, this study also proves that the previously universally accepted theory that the electrophilic nucleophilic duality of free radicals is only determined by their structure is incomplete, and provides compelling evidence to support the hypothesis that regulating the electrophilicity and nucleophilicity of free radicals by changing the reaction conditions can facilitate the synthesis of multiple products from the same precursor material, which means that the atomic economy can be improved when synthesizing products with diverse structures.