Amphiphilic copolymers are receiving increasing attention due to their special features in solubility and self-assembling. Random and block copolymers containing superhydrophobic 2-perfluorooctylethyl acrylate (FA-C8) and superhydrophilic 3-[dimethyl (2′-methacryloyloxyethyl) ammonio] propanesulfonate (MAPS) segments were designed and synthesized in this work, namely PFA-C8-b-PMAPS and P(FA-C8-ran-MAPS). Synthesized polymers were characterized by 1H nuclear magnetic resonance and differential scanning calorimetry (DSC) measurements, proving the achievement of copolymers without residual PFA-C8. The molecular aggregation structure of FA-C8 in PFA-C8-b-PMAPS and P(FA-C8-ran-MAPS) was revealed by DSC and wide-angle X-ray diffraction measurements. On one hand, the PFA-C8 segments in P(FA-C8-b-MAPS) formed hexagonal packing with lamellar structures. On the other hand, although the lamellar structure is not observed in P(FA-C8-ran-MAPS) samples, the hexagonal packing of FA-C8 exhibited higher thermal stability than that of those in the PFA-C8 sample. Moreover, the polymeric film of P(FA-C8-ran-MAPS) exhibited strong oleophobicity under both air and water conditions.