The widespread of drug‐resistant genes has greatly exacerbated the difficulty for the effectively tre atment of diseases associated with bacterial infections. The ineffectiveness of antibiotics poses great challenges to the development of new antimicrobial agents, especially those does not cause bacterial resistance. Herein, a cation porous organic polymer (CPOP) denoted as BDPP, was facilely prepared via the Alder‐Longo method skipping the tedious porphyrin‐bearing monomer synthesis procedure. The repeated porphyrin units endowed excellent photoactivity with the porous skeletons, and the inherent cations significantly improved the binding ability of BDPP with the bacterial cell membrane. As a result, the as‐synthesized POPs could be used as a physical broad spectrum sterilization agent, amalgamating the cation and photothermal therapy to exert synergistic amplified antibacterial effects. In vivo assay demonstrated BDPP with good biocompatibility, could also significantly promote the healing of wounds with bacteria‐infection. This work paves a facile way for the rational construction of material‐based antibacterial agent for the bacteria inactivation.