Phosphorus-containing polymers are particularly attractive for their extensive application in fuel cells, flame retardant, and the biomedical field. Phosphoruscontaining polymers include genetic materials DNA and RNA, and synthetic polymers functionalized at the main chain and those functionalized at the side chain. Vinylphosphonate is one of the simplest vinyl monomers with the phosphonate groups at the side chain. Since the late 1940s, different routes for vinylphosphonate synthesis have been reported. Among these techniques, coordinative-anionic polymerization and living rare earth metal-mediated group transfer polymerization are efficient to generate poly(vinylphosphonates) with higher molecular weight and higher conversions.