Honeycomb-structured porous polymer films based on photosensitizer-grafted polystyrene are prepared through the breath figure process. Rose Bengal (RB) photosensitizer is first attached to a well-defined poly(styrene-stat-4-vinylbenzyl chloride) statistical copolymer, synthesized by nitroxide-mediated radical polymerization. The RB grafted poly(styrene-stat-4-vinylbenzyl chloride) (ca. 20,000 g mol(-1) molar mass, 1.2 dispersity) leads to porous polymer films, with a hexagonal pore pattern, while a simple mixture of poly(styrene-stat-4-vinylbenzyl chloride) and the insoluble RB photosensitizer produced unstructured, nonporous films. The RB-grafted honeycomb films, compared with the corresponding nonporous flat films, are more efficient for oxidation of organic molecules via singlet oxygen production at a liquid/solid interface. The oxidations of 1,5-dihydroxynaphthalene to juglone and α-terpinene to ascaridole are followed in ethanol in the presence of both types of films. Oxidation of the organic molecules is a factor 5 greater with honeycomb compared to the nonporous films. This gain is ascribed to two factors: the specific location of the polar photosensitizer at the film interface and the greater exchange surface, as revealed by fluorescence and scanning electron microscopies.