Functionalization of propane has been investigated using various types of transition metal catalysts in the presence of K(2)S(2)O(8) as oxidant in CF(3)COOH (TFA) solvent. In this reaction the primary products were iso-propyl alcohol and n-propyl alcohol. However, when the reaction was carried out in the TFA solvent, the primary products subsequently reacted with carboxylic acid, yielding iso-propyl trifluoroacetate as the dominant product and n-propyl trifluoroacetate as a minor product. Vanadyl acetylacetonate, VO(acac)(2) ([CH(3)COCH=C(O-)CH(3)](2)VO), exhibited the highest activity for propane functionalization. The optimum reaction conditions were 70 degrees C, 10 mmol of K(2)S(2)O(8), 5 mL of trifluoroacetic acid, 0.1 mmol of catalyst and 0.75 mmol of propane in a 25 mL autoclave. The turn over number was found to be 15.5 and the yield was 1.61 mol% based oil propane when 98 mmol (7 atm) of propane was used in a 200 mL autoclave. The yield was as high as 89 mol% when 0.75 mmol (1 atm) of propane was used in a 25 mL autoclave under optimum reaction conditions.