Polystyrene (PS) initiator was synthesized by atom transfer radical polymerization (ATRP) ,which was introduced to trigger copolymerization of 1H,1H,7H-dodecafluoroheptyl methacrylate(DFHMA). The porous films were prepared by mixing the block copolymer with nano-titanium dioxide(TiO2) via breath figure technique. The structure and properties of PS-b-DFHMA copolymer and porous films were studied. FT-IR, GPC and 1H-NMR were used to characterize the structures, composition and molecular weight of copolymer. The results show that PS-b-PDFHMA copolymer is successfully prepared with controlled structure. Besides, scanning electron microscopy (SEM) was used to characterize the surface morphology of porous films. The wettability and bacterial adhesion of porous films were measured by contact angle and microbial adhesion tests. It suggests that the hydrophilic property of porous films is related to the surface morphology and composition of solution. Those porous films show good hydrophobic performance, and the water contact angle increases to 136° when it is mixed with TiO2, and the amount of bacterial adhesion is declined obviously.