The kinetic polymerization behavior of 2,2,2-trifluoroethyl methacrylate (TFEMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA), 2,2,2-trifluoroethyl acrylate (TFEA) and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) was determined by isothermal differential scanning calorimetry (DSC) and high-performance liquid chromatography (HPLC) in order to improve the properties of fluorinated powder-liquid adhesive resins. Conversion and heat of polymerization were calculated, and the solubility of the homopolymers in common solvents was examined. Comparison of their polymerization reactivity with that of MMA revealed that the overall rate of polymerization initiated by benzoyl peroxide (BPO) decreased in the order TFEA>MMA>TFEMA>HFIPA>HFIPMA. Based on the retention time of the monomer determined by HPLC, the hydrophobicity of the monomers was found to increase in the order MMA<TFEA<TFEMA<HFIPA<HFIPMA. The overall research results suggested that TFEA and HFIPA would be potentially promising candidates for the monomer liquid component of fluorinated powder-liquid adhesive resins.