Stereoselective construction of 3-trifluoromethyl conjugated dienoates, trienoates or dienynoates was achieved from ethyl (Z)-4,4,4-trifluoro-3-iodobutenoate and alkenyltin or alkynyltin reagents through the Stille reaction or under Heck–Sonogashira coupling conditions. Reduction of ethyl 3-trifluoromethyldienoates using DIBAL-H selectively yielded allylic alcohols and hydrolysis with lithium hydroxide yielded the corresponding acids.