AbstractFree radical polymerization of both α‐(trifluoromethyl)acrylic acid (TFMAA) and its methyl ester MTFMA is shown to be possible in the presence of bis(4‐tert‐butylcyclohexyl) peroxycarbonate (Percadox) as initiator and dioxane or THF as solvent. Also it is shown that copolymers of TFMAA with α‐olefins (1‐decene, 2‐methyl‐1‐hexene) and of methyl α‐(trifluoromethyl)acrylate (MTFMA) with vinyl ethers (butyl, 2‐ethylhexyl, and menthyl vinyl ether) can be simply obtained with AIBN as initiator; these copolymers have a predominantly alternating structure.