Infections associated with medical devices have become a major concern. The adhesion of bacteria to the devices' surfaces during the initial 24 h is believed to be a "decisive period" for implant-associated infections, which pose key challenges to optimal antiadhesion of microbes in this period. Herein, we have designed and constructed a (heparin/chitosan)10-(polyvinylpyrrolidone/poly(acrylic acid))10 [(HEP/CHI)10-(PVP/PAA)10] multilayer film by layer-by-layer self-assembly. Assembly of the underlying (HEP/CHI)10 multilayer film is based on electrostatic interactions, showing the properties of contact killing of bacteria. Deposition of the top (PVP/PAA)10 multilayer film is based on hydrogen bond interactions. The PAA molecules are then cross-linked to form anhydride groups by thermal treatment at 110 °C for 16 h. Therefore, it shows a top-down degradable capability in the determined period, leading to almost no adhesion of bacteria in 24 h. Our system combining the adhesion resistance and the contact killing properties shows an enhanced antibacterial capability through targeting the "decisive period" of implantation may have great potential for applications in medical implants, tissue engineering, etc.