Five acrylic esters having different fluorine contents and distributions in their side-groups (i.e., CH2 = CHC(O)OR, where R = -C(CH3)2CrF4H, -C(CH3)2C6F5, -C(CF3)2C6F5, -C(CF3)2C6H5, and -C(CH3)2C6H5) have been prepared from the reactions of the lithium salts of their corresponding alcohols with acryloyl chloride. These monomers are polymerized under identical conditions by the radical initiator AIBN and five polyacrylates were prepared having the structure of -[-CH2CHC(O)OR-]n-. These addition polymers were compared and fully characterized by GPC, VPO, DSC, TGA, NMR, IR, and UV-visible spectroscopies, and they showed potential for practical applications. Significant differences in their thermal stabilities were found with respect to fluorine contents and distributions in these polyacrylates, and the highest stability arises from CF3 substitutions in the side-chains of the polymers.