The first catalytic trifluoromethoxylation of unactivated alkenes has been developed, in which Pd(CH3CN)(2)Cl-2 was used as catalyst, AgOCF3 as trifluoromethoxide source, and Selectfluor-BF4 as oxidant. A variety of 3-OCF3 substituted piperidines were selectively obtained in good yields. Direct evidence was provided to address the facile reductive elimination of Pe(IV)-OCF3 complex to form sp(3) C-OCF3 bond.