Microporous films consisting of two-dimensionally ordered void structures - so-called honeycomb films - were produced by evaporation of polymer solutions under high humidity. Two types of poly(vinyl cinnamate)s were used: A newly synthesized amphiphilic poly(vinyl cinnamate) and a mixture of a commercial poly(vinyl cinnamate) and an amphiphilic poly-ion complex. Photo-crosslinking of the honeycomb structure could be achieved by UV irradiation while completely retaining the film morphology. The crosslinked films showed excellent stability against organic solvents.