The broad utilization of fluorinated compounds in agrochemicals, pharmaceuticals, and materials science 1 has spurred considerable endeavors to develop efficient methods for selectively introducing fluorinated moieties into organic molecules. 2 Among these, the difluoromethyl group (CF2H), acting as a bioisostere of hydroxyl and thiol groups while serving as a lipophilic hydrogen bond donor, has gained significant attention in pharmaceutical and agrochemical domains. 3 The incorporation of C(sp 3 )-CF2H profoundly enhances metabolic stability, oral bioavailability, and solubility in comparison to their non-fluorinated counterparts, prevalent in numerous bioactive compounds (Figure ). 4 Consequently, difluoromethylation stands as a potent strategy for modulating the biological activity and solubility of bioactive compounds. Difluoromethylation reactions have made substantial strides in recent decades, employing nucleophilic, electrophilic, and free-radical intermediates. 5 The advent of photoredox catalysis offers a greener and more sustainable avenue for generating difluoromethyl radicals. 6 However, prevailing methodologies often necessitate expensive reagents or multifaceted building block synthesis. 7 Notably, widely-used CF2H radical precursors, such as HCF2SO2Cl and its difluoromethylsulfinate derivatives, are derived from ClCF2H through a sequence of steps. 8 Chlorodifluoromethane (ClCF2H), commonly known as Freon-22, serves as a prolific industrial feedstock crucial for synthesizing various fluorinated polymers, including Teflon and polyvinylidene fluoride. 9 Despite the prohibition of Freon-22 in current production practices, substantial quantities persist in storage and legacy air conditioning systems. Consequently, devising methodologies for the transformation of Freon-22 into environmentally benign and valuable compounds has become imperative for addressing environmental concerns. However, ClCF2H's organic transformations are notably constrained by its subdued reactivity, primarily involving intermediates of difluorocarbene that engage with heteroatom nucleophiles (O, S, N, P) to afford corresponding heteroatom-substituted difluoromethylated products. 10 Significantly, the Zhang group has ingeniously harnessed difluorocarbene through palladium catalysis, enabling cross-coupling reactions with both nucleophiles and electrophiles to forge C(sp 2 )-CF2H or C(sp)-CF2H bonds. 11 In contrast, the exploration of Freon-22 as a difluoromethyl radical precursor remains in its infancy (Figure ). In fact, only two instances of CF2H radical generation from Freon-22 are reported. In 2018, the Zhang group achieved nickel-catalyzed difluoromethylation of (hetero)aryl chlorides and bromides with ClCF2H via a radical mechanism employing zinc as a reductant. 12 In 2022, the Wu group showcased the efficient generation of CF2H radicals from ClCF2H through photoredox catalysis, coupled with ligated tertiary amine boranes, enabling selective halogen atom transfer (XAT) and effecting hydrodifluoromethylation of inert alkenes. 13 As such, the quest for innovative catalytic systems to harness CF2H radicals from Freon-22 persists as a highly desirable frontier.