In summary, the first efficient access to Het-NCF2H complex products featuring either imine and/or ketone moieties was unlocked herein. The methodology utilizes inexpensive, commercially available, and bench-stable bromo(difluoro)acetic acid as a difluoromethylating agent with K2CO3 as a base. Depending on the type of nitrogen heterocycle, this approach also permits the incorporation of two CF2H units. The key to accomplishing the aforementioned products is the increased nucleophilicity and reduced steric hindrance on the nitrogen atom of the heteroarene ring. The ambient reaction conditions and high chemoselectivity have permitted the difluoromethylation of >70 privileged N-heterocyclic substrates (e.g., derivatives of quinolines, quinazolines, pyridines, lactams, etc.), including 18 commercial drugs. In addition, this streamlined approach can run up to a 142-mmol scale (>50 g) with exceptional inclusion of the CF2H group in 1a comprising the imine unit. Mechanistic investigations concluded that Ndifluoromethylquinolinium salt serves as a key intermediate for the decarboxylative N-difluoromethylation with bromo(difluoro)acetic acid. In the end, for the first time, we have successfully proven the rapid hydrodefluorinative reduction in a single step, utilizing it to construct a complex N-methylated Fsp 3 -enriched scaffold. We anticipate this comprehensive cost-effective strategy significantly expands the drug-like chemical space accessible to smallmolecule N-difluoromethylated compounds.