Honeycomb-patterned polymer films prepared by the breath figure method exhibit unique shape features. These films have potential in various applications, but functional materials are rarely embedded into the arrayed cavity. Here, a photoswitchable function of a compartmented nematic liquid crystal (NLC) in a honeycomb array is proposed. Surface segregation and liquid crystal self-assembly processes cover curved honeycomb walls of polystyrene (PS) with a high-density polymer brush of an azobenzene side chain liquid crystalline polymer (SCLCP), producing honeycomb polymer films with isolated cavities. Spherical confinement of the cavities with the SCLC brush provides a bipolar nematic director (planar anchoring), whereas UV light irradiation induces a radial configuration (homeotropic anchoring) of NLC droplets. Photoisomerization of azobenzene UV and visible light irradiation repeatedly induces a photoswitchable change between the bipolar and radial modes.