The novel P–N ligand 1-((diphenylphosphaneyl)methyl)-1H-benzo-1,2,3-triazole (1), based on a benzotriazole scaffold, has been prepared. The reaction of 1 with [CoCp*(CH₃CN)₃][BF₄]₂ and [CoCp*(I)₂]₂ (Cp* = pentamethylcyclopentadienyl) affords the chelate complexes [CoCp*(CH₃CN)(P–N)][BF₄]₂ (2) and [CoCp*(I)(P–N)]I (3), respectively. Complexes 2 and 3 were studied as catalysts in the fluorination of aromatic and aliphatic acyl chlorides in CH₂Cl₂, with 3 showing notably higher activities than 2. Subsequently, organic carbonates (dimethyl carbonate and propylene carbonate) were also employed as solvents, which led to shorter reaction times and to the broadening of the substrate scope to a variety of aliphatic halides. Comparative studies between 3 and the analogous complex [CoCp*(I)₂(PMePh₂)], which features a monodentate phosphane ligand, showed that higher yields were obtained in the case of the former. DFT calculations and experimental studies were performed in order to shed light on the reaction mechanism, which entails the formation of a cobalt fluoride species that reacts via nucleophilic attack with the substrate to afford the corresponding fluorinated compounds.