Biomass-derived furfuryl methacrylate (FMA) has been successfully polymerized for the first time by anionic polymerization to produce atactic (at-), isotactic (it-), or syndiotactic (st-) poly(furfuryl methacrylate) (PFMA), depending on initiator structure and reaction conditions. Thermal properties of the PFMA materials are strongly affected by the polymer tacticity. Most notably, while both isotactic and syndiotactic polymers can undergo inter- or intrachain crosslinking reactions when heated to 290 degrees C, there is no evidence for the atactic polymer to perform the same reaction. Furthermore, the PFMA tacticity also greatly affects the amount of stable carbonaceous materials it produces when heated to 650 degrees C, with st-PFMA forming the largest amount of such materials (26.9%), as compared to only 5.6% by at-PFMA. Using the Diels-Alder (DA) click reaction between the reactive furfuryl group within the PFMA polymers as the diene equivalent and a bismaleimide as the dienophile, thermoreversible smart polymers have been successfully prepared. Thermoreversibility of the preformed crosslinked polymers has been demonstrated, thanks to the facile retro-DA reaction upon heating and the DA reaction upon cooling of such self-healing materials. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2793-2803