Perfluoro epoxy compounds are important intermediates in organic chemistry, however, the methods for preparing them are scanty. We found that in situ generated tri-n-butylamine N-oxide and N,N-Dimethylcyclohexylamine N-oxide were found to be good reagents for the epoxidation of tri-substituted Perfluoro-2-methyl-2-pentene in good to excellent yields. Catalytic epoxidation methods were developed by coupling this reaction with the N-oxidation of tertiary amine by hydrogen peroxide or MCPBA. The advantages of these methods are easy work-up, mild reaction conditions, environmentally friendly and low cost. The reaction using MCPBA as a oxidant is better than hydrogen peroxide for it is fast and high yielding.