AbstractThe copolymerizations of l‐menthyl vinyl ether (l‐MVE) with the monomers, that is, maleic anhydride (MAn), dimethyl maleate (DMM), and dimethyl fumarate (DMFu), were undertaken to obtain optically active copolymers. The optically active l‐menthyl group in the side chain of copolymers was removed by the ether cleavage reaction with dry‐hydrogen bromide gas. The ethercloven copolymers were still optically active. Hence it was concluded that asymmetric carbon atoms were introduced into the copolymer main chain, the reason given being that l‐MVE and comonomers (MAn, DMM, and DMFu) made the stereoselective charge‐transfer complex one another and copolymerized stereospecifically. From the results of the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) for copolymers before and after the ether cleavage reaction, the mode of bond opening for α,β‐substituted monomers (MAn, DMM, and DMFu) was discussed and the microstructures of copolymers were prepared.