In this paper, we demonstrated the successful fabrication of crosslinked porous films with varying monomer-crosslinker ratios, by photo-induced crosslinking during the breath figure formation. For all the samples fabricated, the pores at the peripheral regions appeared more uniform in size and showed higher degree of ordering, due to the interplay between the solvent evaporation and crosslinking reaction. The pore morphology remains similar despite varying film compositions, suggesting that the pore-fixing process is still dominated by the solvent evaporation similar to that of conventional breath figure process, and is less dependent on the crosslinking process. Detailed characterizations of the chemical and physical properties, including the glass transition temperature, thermal stability, and surface wettability of the porous films were carried out.