New brush polymers with various numbers of bristle ends incorporating phosphorylcholine (PC) moieties are synthesized. The polymers are thermally stable up to 175 °C and form good-quality films with conventional spin-, roll-, and dip-coating, and subsequent drying processes. Interestingly, all these brush polymers, as a PC-containing polymer, demonstrate a stable molecular multi-bilayer structure in thin films that arise due to the efficient self-assembly of the bristles for temperatures <55 °C and PC-rich surfaces, and therefore successfully mimic natural cell-membrane surfaces. These brush-polymer films exhibit excellent water wettability and water sorption whilst retaining the remarkable molecular multi-bilayer structure, and thus have hydrophilic surfaces. These novel multi-bilayer structured films repel fibrinogen molecules and platelets from their surfaces but also have bactericidal effects on bacteria. Moreover, the brush-polymer films are found to provide comfortable surface environments for the successful anchoring and growth of HEp-2 cells, and to exhibit excellent biocompatibility in mice. These newly developed brush polymers are suitable for use in biomedical applications including medical devices and biosensors that require biocompatibility and the reduced possibility of post-operative infection.