Herein, we report the transformation of beta-monomethyl itaconate, an inexpensive and biorenewable alternative to petroleum feedstocks, to the high-value monomer alpha-methylene-gamma,gamma-dimethyl-gamma-butyrolactone (Me2MBL) through a selective addition strategy. This strategy is also applied to the synthesis of alpha-methylene-gamma-butyrolactone (MBL, tulipalin A), a monomer that can be polymerized to give materials with desirable properties (high decomposition temperature, glass transition temperature, and refractive index). Subsequent polymerization of both Me2MBL and MBL through reversible addition-fragmentation chain-transfer polymerization generates well-defined poly(Me2MBL) and poly(MBL) (PMBL). Physical characterization of poly(Me2MBL) shows good physical properties comparable with known PMBL materials. (C) 2017 Wiley Periodicals, Inc.