A new protocol has been developed for the borylation of conjugated alkenyl methyl ethers using B 2 Pin 2 via C−O bond cleavage catalyzed by Ni(II). In this cross-coupling reaction, both E/Z isomers of alkenyl ethers are converted into (E)-alkenyl boronic esters with good reactivity. This transformation exhibits high chemoselectivity in the presence of competitive C−O bonds such as aryl ether, ester, amide, and thioether groups, thus providing a new method for the construction of various alkenyl boronates.