As a novel synthetic strategy for copolymers of vinyl alcohol, we propose herein copolymerization of alkoxyvinylsilanes with other vinyl monomers, followed by oxidative cleavage of the alkoxysilyl groups attached to the main chain of the resulting copolymers. Radical copolymerization of di(isobutoxy)methylvinylsilane 1 with styrene afforded poly(1-ran-styrene)s with a variety of compositions of both repeating units, although the M-n's (<9000) and yields (<35%) were rather low. The oxidative cleavage of the alkoxysilyl groups in the copolymers with m-chloroperbenzoic acid proceeded efficiently, giving poly(vinyl alcohol-ran-styrene)s, which were soluble in common organic solvents. The structures of the poly(vinyl alcohol-ran-styrene)s were characterized by NMR, GPC, elemental analysis, and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS). (C) 2007 Wiley Periodicals, Inc.