Pathogenic bacteria adhesion and formation of biofilm on the implant are the most common reasons for healthcare-associated device failure. Cationic amphiphilic polymer brushes containing covalently linked quaternary ammonium salts (QASs) are considered to be the most promising bactericidal materials, but these surfaces still suffer from incomplete bactericidal ability and serious microorganism accumulation. With this in mind, a novel kind of hierarchical surface integrating both geminized cationic amphiphilic antibacterial upper layer and zwitterionic antifouling sublayer has been developed in this study. Measurements of X-ray photoelectron spectroscopy, spectroscopic ellipsometry, atomic force microscopy, water contact angle, and surface zeta-potential were performed to investigate the surface functionalization process. The thicknesses and grafting densities of the pAGC8 upper blocks have been optimized to avert the mutual interference among different components. The optimal hierarchical surface exhibits an ultrahigh antibacterial activity and a potent self-cleaning functionality against both Staphylococcus aureus and Escherichia coli bacteria, as well as a certain protein repellence ability. Such a novel hierarchical architecture provides innovative guidance for the construction of super-antibacterial and self-cleaning brushes in many biomedical applications.