Multifaceted porous materials were prepared through careful design of star polymer functionality and properties. Functionalized core crosslinked star (CCS) polymers with a low glass transition temperature (T-g) based on poly(methyl acrylate) were prepared having a multitude of hydroxyl groups at the chain ends. Modification of these chain ends with 9-anthracene carbonyl chloride introduces the ability to reversibly photocrosslink these systems after the star polymers were self-assembled by the breath figure technique to create porous, micro-structured films. The properties of the low T-g CCS polymer allow for the formation of porous films on non-planar substrates without cracking and photo-crosslinking allows the creation of stabilized honeycomb films while also permitting a secondary level of patterning on the film, using photo-lithographic techniques. These multifaceted porous polymer films represent a new generation of well-defined, 3D microstructures.