Microbial infections continue to be one of the cosmopolitan safety hazards to humankind. To achieve effective sterilization, it is urgent to develop non-antibiotic strategies or integrating multiple antimicrobial methods. Organic photo-antimicrobials (OPAMs) has attracted attention in fighting against bacteria by reactive oxygen species (ROS) or heat without triggering drug resistance. In our work, a copper-porphyrin doping donor-acceptor (D-A) type covalent organic framework (COF), named CTF-BTA2OH-Por(Cu), is constructed to achieve synergistic antibacterial effects by ROS generation and protein degradation. Copper-porphyrin doping improves ROS generation of D-A COF, showing great photocatalytic antibacterial activity (>90 % within 1 h). Additionally, the polyphenolic aldehydes of BTA2OH can interact with protein strongly and cause degradation, resulting inhibition of bacteria growth without light. Thus, CTF-BTA2OH-Por(Cu) showed antibacterial activity under both light and dark conditions. These findings give inspiration for COF multifunctional design for antimicrobials strategy and its application in supplies anti-infection or preservation.