Transition metal-catalyzed selective radical difunctionalization of 1,3-dienes has emerged as a pivotal approach for synthesizing intricately functionalized molecules. 14 In this context, the direct utilization of CF2HCl within a multicomponent reaction to functionalize conjugated dienes presents a compelling avenue to access polyfunctionalized alkene molecules bearing CF2H groups which remains an unsolved challenge. The hybrid palladium catalysis has recently showcased its prowess in efficiently reducing various C-X (X = F, Cl, Br, I) bonds through single electron transfer, harnessing both radical and polar reactivity. 15 Motivated by the ongoing interest in radical-polar crossover pathways for multicomponent reactions, 16 we question whether hybrid palladium catalysis can facilitate the regioselective difunctionalization of conjugated dienes via direct reduction of Freon-22 to generate CF2H radicals. Here, we unveil the successful execution of hybrid palladium-catalyzed difluoromethylamination of conjugated dienes, employing ClCF2H as the CF2H radical precursor, resulting in exclusive 1,4-regioselectivity. This redox-neutral transformation unfolds under mild conditions, offers an expansive substrate scope, and represents the inaugural instance of CF2H radical generation from Freon-22 via palladium catalysis. To validate our hypotheses, we employed (E)-nona-1,3diene a as the model substrate, ClCF2H as the CF2H radical precursor, and morpholine b as the nucleophile to systematically optimize reaction conditions within an excited palladium catalytic framework (Table ). Gratifyingly, under blue LED irradiation at room temperature, using Pd(PPh3)4 (5 mol %) as photocatalyst, K3PO4 as the base, and DMSO as the solvent, the reaction smoothly delivered the desired product 3c in 20% yield (entry 1). Alternative solvents, such as PhF and CH3CN, resulted in reduced yields (entries 2-3), thereby confirming DMSO's optimal role. Among evaluated bases, only potassiumbased ones facilitated the desired product formation (entries 5-8). Elevating the catalyst loading to 10 mol % boosted the yield to 84%, accompanied by . Importantly, across all instances, carbene insertion of NH product was conspicuously absent. Control experiments highlighted the indispensability of both palladium catalyst and light within this hybrid palladium-catalyzed system (entries 12-14). Notably, using 3 eq ClHCF2 instead of balloon could achieve 75% yield (entry . Ultimately, the optimized conditions were established as follows: Pd(PPh3)4 (10 mol %), a (1.5 eq), and b (1.0 eq) in DMSO (0.1 M) at room temperature under 1 atm Freon-22 and 456 nm blue LED light irradiation ( a General conditions (unless otherwise specified): 1 (0.5 mmol), 2 (0.2 mmol), ClCF2H (balloon), Pd(PPh3)4 (0.02 mmol), K3PO4 (0.3 mmol), solvent (4.0 mL), 455-460 nm blue LED with fan, rt, 8 h. b Isolated yield of 3. c Without light. d with 40% PPh3 as catalyst. e with 3 eq ClCHF2. f with 5 eq ClCHF2.