A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement,X-ray photoelectron spectroscopy(XPS),sum frequency generation(SFG) vibrational spectroscopy,surface tension and dynamic laser light scattering(DLS).It was found that with increasing PFMA block length,water and oil repellency de-creased,the ratio of F/C increased with increasing film depth,and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased.When the number of PFMA block units reached 10,PMMA segments were detected at the copolymer surface,which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface,which in turn affects surface structure formation during solution solidification.The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface. A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late (PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization (ATRP). The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement, X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy, surface tension and dynamic laser light scattering (DLS) .It was found that with increasing PFMA block length, water and oil repellency de-creased, the ratio of F / C increased with increasing film depth, and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased. WHEN the number of PFMA block units reached 10, PMMA segments were detected at the copolymer surface, which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air / liquid interface, which in turn affects surface structure formation during solution solidification. The results suggest that copolymer solution properties play an important role in structure formation on the solid surface.