Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However,the influence of the non-fluorinated block on the surface structure of the copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl methacrylate (FMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS),sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid interface,which favors the -(CF2)7CF3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers,in addition to the fluorinated monomer content,plays an important role in structure formation on the solid surface. Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However, the influence of the non-fluorinated monomers on the surface structure of the copolymer is unknown. (PBMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyzes that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed m ainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air / liquid interface, which favors the - (CF2) 7CF3 moieties self-assembling on the polymer surface during film formation . This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers, in addition to the fluorinated monomer content, plays an important role in structure formation on the solid surface.