Novel poly(hydroxypropyl acrylate)-co-poly(hydroxypropyl acrylate)-rhodamine B (PHPA-co-PHPA-RhB) hydrophilic copolymers were synthesized via radical polymerization in this paper. And then the honeycomb-structured porous films were fabricated by dropping the (PHPA-co-PHPA-RhB) copolymers and PS solution on glass substrates by breath figure method (BFM). The effects of solvent, hydrophilic copolymers' molecular weight, the proportion of hydrophilic copolymers and hydrophobic polymers on the formation of porous films were investigated. The porous films were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), spectrofluorometer and confocal laser scanning microscope (CLSM). The results show that PHPA-co-PHPA-RhB and PS solutions can form regular honeycomb porous films; the average diameter of the films pore decreases with the proportion of hydrophobic polystyrene increased. Similar regular was also found when the molecular weight of PHPA-co-PHPA-RhB was enhanced. Furthermore, the fluorescence properties of the porous films were also investigated in this study.