To elucidate the underlying mechanism governing the radical difluoromethyl difunctionalization of 1,3-dienes, we conducted the standard reaction in the presence of the radical scavenger (TEMPO) (Figure ), and only 8% of the difluoromethyl radical adduct product with TEMPO (e) was detected by 19 F NMR. The Stern-Volmer luminescence quenching experiments was then conducted to discern the interaction of Pd(0)* with various components. Only Freon-22 exhibited substantial quenching of Pd(0)*, unlike substrates a and b, as depicted in Figure . Drawing from mechanistic insights and precedent literature, we propose the subsequent reaction mechanism (Figure ). Initially, upon photoexcitation, LnPd 0 engages in a single electron transfer (SET) with Freon-22, yielding the difluoromethyl radical and LnPd I . The latter species adds to the terminal position of the diene, generating radical species I, which in turn, combined with LnPd I to form the intermediate II. Finally, a nucleophilic substitution facilitated by the amine happens to afford the 1,4-addition product 3c. This process leads to the formation of the difunctionalization product and the regeneration of the palladium catalyst. In summary, we have established the first example of employing visible-light-induced palladium catalysis to attain the difluoromethylation of 1,3-dienes through the utilization of Freon-22. This innovative approach embraces a diverse array of amines, sodium sulfinates and enolate as nucleophilic partners, effectively delivering the exclusive 1,4-difunctionalization products with E-geometry double bond. The multicomponent coupling reaction, characterized by its mild reaction conditions, wide functional group tolerance, and excellent regioselectivity, holds promise for the late-stage functionalization of intricate molecules and pharmaceutical compounds. The gram scale reaction also highlights the utility of this method to quickly assemble industrial stocks into valuable complex organic molecules. Initial mechanistic insights highlight the significance of a radical-polar crossover pathway in enabling this transformation. Our methodology not only introduces a modular, versatile, and gentle strategy for synthesizing polyfunctionalized alkenes with CF2H but also provides a promising avenue for repurposing Freon-22.