Here we report on the coordination polymerization of a vinyl-functionalized butadiene monomer, 3-methylenehepta-1,6-diene (MHD) with exclusive conjugated diene chemoselectivity, high 1,2-regioselectivity and moderate isotacticity (1,2-selectivity>99%, mm triad=93%). Random copolymers of MHD and other conjugated diene (isoprene or myrcene) are also synthesized. The pendent vinyl groups of MHD homo or copolymers could be quantitatively converted into various functional groups via thiol-ene click reaction. The resulting functionalized polybutadiene-based material display versatile thermal and surface properties. (C) 2017 Wiley Periodicals, Inc.