New Pt(IV) perfluorocarboxylate complexes of the composition [Pt(RFCOO)4]n and M2[Pt(RFCOO)6] (RF = CF3, C2F5; M = Li, Na, K, Rb, Cs, NMe4) have been synthesized and studied. These complexes are strong oxidizing agents capable of oxidizing alkanes in trifluoroacetic acid under mild conditions to form trifluoroacetic acid esters and acting as catalysts for the oxidative trifluoroacetoxylation of alkanes, cycloalkanes, and framework compounds. They can also be used as starting compounds for the synthesis of other perfluorocarboxylate complexes of platinum in various oxidation states. The structure of (NMe4)2[Pt(CF3COO)6] · 6CF3COOH has been determined by X-ray diffraction.