AbstractMethyl α‐(alkoxymethyl)acrylates were prepared from methyl α‐(bromomethyl)acrylate in 80–90% yield. The monomers homopolymerize fast to yield low‐molecular‐weight polymers. The monomers bearing a linear alkoxymethyl group except for the ethoxymethyl group are characterized by a relatively low ceiling temperature. The rate constants for propagationkpand terminationktof methyl α‐(butoxymethyl)acrylate were evaluated to bekp= 298 dm3· mol−1· s−1andkt= 8 · 106dm3· mol−1· s−1at 60°C, respectively. The α‐(alkoxymethyl)acrylates are more reactive than methyl methacrylate toward polystyrene radical, except for the α‐(dodecyloxymethyl)acrylate which is slightly less reactive, indicating that an increase in the reactivity by the electron‐withdrawing character of the alkoxy group prevails over the steric hindrance against addition of the polymer radical, except