Chitosan exhibits remarkable broad-spectrum antibacterial activity, especially in acidic environments. However, its poor solubility in water and significantly decreased antibacterial performance after membrane formation greatly limit its extensive application. To address this issue, glycol chitosan-4-pyridylcarboxaldehydeborneol (GCBP) was synthesized by conjugating glycol chitosan (GC) with 4-pyridylcarboxaldehydeborneol ester (BP) through dynamic Schiff base bonds utilizing a layer-by-layer self-assembly strategy. When bacteria come into contact with the surface, the local acidic microenvironment triggers the cleavage of the Schiff base, resulting in the release of bactericidal BP and GC for combined sterilization. In vitro results demonstrated that the antibacterial properties of GCBP were positively related to the modification layers. The excellent antibacterial performance of the GCBP modification demonstrates not only great potential for clinical urinary catheters but also for broad antibacterial applications in the medical field.