Bacterial infection on biomaterial devices and the subsequent medical risks pose a serious problem in both human healthcare and industrial applications, resulting in a prevalence of various antimicrobial materials. Cationic amphiphilic polymer has been proposed to be a new generation of efficient antibacterial material, but the surface modified by such types of polymers still shows incomplete bactericidal ability and easily contaminated performance. With this in mind, a novel kind of geminized cationic amphiphilic polymer brush surface has been developed in this study, presenting a complete antibacterial activity, because of the synergistic biocidal effect of electrostatic and hydrophobic interactions, as well as the minimized contact area between bacteria and polymer surface. A structure self-adjustment process of polymer brush construction has been proposed, in which the mutual interference among cationic head groups can be avoided and the electrostatic repulsion and hydrophobic attraction can be balanced, in the formation of a smooth and tight surface. A self-cleaning capability of polymer surface has been performed via hydrolysis and degradation, maintaining a high antibacterial activity. Therefore, we provide a facile and possible manipulation strategy to fabricate super-antibacterial and self-cleaning surfaces in a wide range of biomedical and industrial applications.