Itaconates containing a 1-adamantyl or a 3,5-dimethyl-1-adamantyl ester group were prepared and polymerized in the presence of a radical initiator. The polymerization reactivity has been investigated in relation to the structure of ester alkyl groups of the monomer. It has been clarified that the adamantyl-containing polyitaconates show high thermal stability, i.e., high glass transition temperatures and decomposition temperatures. The relationship between polymer structures and thermal properties of polymers from some alpha- and beta-substituted acrylic esters, i.e., acrylates, methacrylates, crotonates, fumarates, and itaconates was discussed.