Nickel perfluoroethyl and perfluoropropyl complexes supported by naphthyridine-type ligands show drastically different aerobic reactivity from their trifluoromethyl analogs resulting in facile oxygen transfer to perfluoroalkyl groups or oxygenation of external organic substrates (phosphines, sulfides, alkenes and alcohols) using O 2 or air as a terminal oxidant. Such mild aerobic oxygenation occurs through the formation of spectroscopically detected transient high-valent Ni III and structurally characterized mixed-valent Ni II -Ni IV intermediates and radical intermediates, resembling O 2 activation reported for some Pd dialkyl complexes. This reactivity is in contrast with the aerobic oxidation of naphthyridine-based Ni(CF 3 ) 2 complexes resulting in the formation of a stable Ni III product, which is attributed to the effect of greater steric congestion imposed by longer perfluoroalkyl chains. Aerobic oxidation of long-chain perfluoroalkyl Ni complexes results in O-atom transfer to form perfluorocarboxylates via high valent Ni; in the presence of external substrate, oxygenation of phosphines, sulfides, stilbenes or alcohols occurs.