A new photochemically bifunctional epoxy and dimethacrylate compounds were synthesized for investigating the photosensitivity under UV irradiation. Photosensitivity of the synthesized chalcone-based compounds was investigated by using UV-visible absorption and Fourier transformed infrared (FT-IR) spectroscopies. The result of spectroscopic analysis substantiated that the two chalcone-based compounds have functions of both photocrosslinking and photopolymerization by UV exposure in the presence of photoinitiator. Two kinds of photochemical reactions proceeded competitively during UV exposure. Particularly, we studied the effect of photopolymerization on the rate of photocrosslink due to cycloaddition in the two oligomeric compounds.