Bacterial infection poses a significant threat to clinical treatment due to the emergence of drug resistance and the high risk of recurrence. Here, we report the de novo design of a spiky pollen-based vanadium artificial enzyme particle (VAE-Pollen) that integrates potent reactive oxygen species (ROS)-catalytic activity with immune priming to prevent both primary and secondary bacterial infections. Experimental and theoretical analyses confirm that bacteria are efficiently captured by the micro-structured surface of VAE-Pollen, and the introduction of oxygen vacancies modulates the electronic configuration of vanadium catalytic sites, significantly enhancing their versatile ROS-catalytic performance. Meanwhile, VAE-Pollen enhances bacterial capture and ROS-triggered release of bacterial antigens, which mimics the sustained allergen exposure characteristic of natural pollen, thereby potently activating systemic defensive responses and providing sustained anti-infective surveillance to prevent secondary wound infection. Notably, the VAE-Pollen demonstrates significant efficacy in treating methicillin-resistant Staphylococcus aureus (MRSA) and preventing its recurrence, offering a potent and intelligent antibacterial alternative that may circumvent the limitations of conventional antibiotics.