A stereospecific deoxygenation of trans-epoxy cinnamic acid derivatives to access (Z)-cinnamamides, (Z)-cinnamyl alcohol and (Z)-cinnamyl amines using a catalytic system based on nickel triflate and triphenylphosphine has been developed. The desired products were obtained in good to excellent yield (up to 92 % isolated yield) and excellent stereospecificity (Z: E ratio up to>99: 1). The transformation has a broad functional group tolerance including amides, amines, alcohols and esters. The power of the methodology was demonstrated in the key step of the total synthesis of biologically active natural product, N-cis-feruloyl tyramine from readily available trans-ferulic acid. A reaction mechanism involving activation of epoxide via coordination of the oxygen atom and the neighboring O- or N-atoms to the nickel catalyst and formation of Ph3P-carbon bond is proposed. This method is important for synthesis of highly desirable functionalized (Z)-alkenes from readily available (E)-alkenes.