Functionalized vinyl cinnamate monomers were synthesized by the reaction between hydroxyethylacrylate (HEA) and substituted cinnamoyl chlorides possessing electron releasing and withdrawing functional groups like chloro, methoxy, and nitro groups at the para position of the aromatic ring. The structures of these monomers were characterized by Fourier transform infrared (FTIR), 1H-, and 13C-NMR spectral techniques. The homopolymers of the synthesized monomers were obtained by the free radical solution polymerization in dimethylformamide (DMF) at 80