Periodic copolymers of ethylene and vinyl alcohol (EVA) were synthesized via acyclic diene metathesis (ADMET) polymerization of a series of structurally symmetric alpha,omega-diene monomers that containing two vinyl acetate (VAc) units, followed by exhaustive hydrogenation and subsequent hydrolysis. This synthetic methodology provided a new type of EVA copolymer with defined sequence and ever highest VA content via ADMET. These polymer samples were characterized by gel permeation chromatography (GPC), NMR, and matrix-assisted laser desorption/ionization time-of-fight mass spectroscopy (MALDI-TOF-MS). Thermal properties of EVAc and EVA copolymers were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). EVAc copolymers exhibited two-stage decompositions on TGA traces and displayed a glass transition on DSC thermograms. Meanwhile, the EVA copolymers showed glass transition stages and sharp melting peaks on DSC thermograms, with the T-m values being comparable to that of high density polyethylene (HDPE). (C) 2013 Elsevier Ltd. All rights reserved.