Copolymerization reactions of butadiene oxide (BuO) with 3-glycidyloxypropyltrimethoxysilane (GPTS) and styrene oxide (SO) were carried out under solvent free condition by potassium hydroxide catalyst. Copolymers obtained from ring opening polymerization of BuO with GPTS and SO were characterized by H-1-NMR, C-13-NMR, FTIR, DSC, and gel permeation chromatography. High-resolution NMR analysis was particularly effective in the study of copolymers microstructures and revealed the structural and sequence details. Block copolymers were formed because of different polymerization velocity of monomers. Average molecular weights of copolymers were between 1500-13 000 Da and polydispersity index of copolymers is rather low (M-w/M-n = 1.17-1.36). Copolymers were hydrolyzed by 1.0 M tetrapropylammonium hydroxide to form copolyglycol having adhesive and fiber characteristics. (c) 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47074.