In this protocol, the chemoselective defluoromethoxylation reactions of 2-trifluoromethyl-1,3-enynes were developed. The enynic and allenic orthoesters were selectively produced in good to excellent yields via multiple substitution processes under mild reaction conditions, respectively. The enynic orthoester products were proved capable of acting as efficient "platform molecules" to access various functionalized allenyl compounds.