have fabricated C-O, C-Br, C-I, C-C, and C-N bonds with high selectivity using a copper catalyst at elevated temperatures . Thus, it is well established, theoretically and practically, that the electrophilic-nucleophilic bias of free radicals depends on their structure and that free radicals are either electrophilic or nucleophilic during organic reactions. Therefore, it is natural to explore if this bias can be regulated by changing the reaction conditions. If this regulation is achieved, the opportunity for free radicals to undergo novel reactions can be doubly enhanced. To achieve this objective, we envisioned the development of distinct synthetic protocols to regulate the electrophilic-nucleophilic bias of free radicals for the synthesis of multiply substituted quinolines in a productive fashion. Further, we wanted to extend the addition reactions of α, β-unsaturated ketones, namely Michael addition and anti-Michael addition , to involve free radicals as substrates. In this regard, the imine C-H bond of (E)-3-(2-(((E)-benzylidene)amino)phenyl)acrylate was photoactivated to obtain the imine carbon radical. The addition of N,N-dimethylpyridin-4-amine (DMAP) facilitated the electrophilic attack of the imine carbon free radical on the α position of the acrylate to form 2,3-disubstituted quinolines via intramolecular cyclisation. In contrast, the addition of lithium hydroxide (LiOH) facilitated the nucleophilic attack of the imine carbon free radical on the β position of the acrylate to form 3,4-disubstituted quinolines via a complicated rearrangement. These methods for the synthesis of poly-substituted quinolines exhibit various advantages, such as, mild reaction conditions, facile and simple setup and operation, biodegradability, and a good functional group tolerance. The reaction mechanisms explored in this study are proposed based on theoretical calculations and experimental observations. The examples discussed in this work demonstrate the possibility of regulating the electrophilicity and nucleophilicity of free radicals via changes in the reaction conditions and suggest novel opportunities for free-radical addition reactions.