An asymmetric bifunctional monomer having both an unprotected alkynyl group and a vinyl ether (VE) group (3-[2-(2-vinyloxyethoxy)-ethoxy]-propyne [VEEP]) was newly designed and found that the polymerization of VEEP smoothly proceeded in a controlled manner under a living cationic polymerization condition to give alkyne-substituted polyVE (polyVEEP) without any protection of the pendant alkynyl function. Next, the use of an initiator with a methacryloyl moiety for the living cationic polymerization of VEEP afforded macromonomer-type polyVE (MA-PVEEP) carrying pendant alkynyl groups. The potential ability of the resultant macromonomer as an alkyne-substituted polymer for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) was also confirmed. A novel macromonomer-type glycopolymer [MA-P(VE-Mal)] having pendant maltose residues and a terminal methacryloyl group was successfully synthesized by CuAAC of MA-PVEEP with maltosyl azide. Thus, a new pathway to the controlled synthesis of macromonomer-type glycopolymers of free from any protecting/deprotecting processes was demonstrated. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 681-688