Controllable and on‐demand delivery of supramolecular systems have received considerable attention in modern agricultural management, especially for managing intractable plant diseases. Here, an intelligent photoresponsive pesticide delivery system is reported based on β‐cyclodextrin (β‐CD) and azobenzene, which overcomes the resistance of phytopathogens caused by the irrational use of conventional pesticides. Antibacterial bioassays illustrated that designed azobenzene derivative 3a possesses the most efficient bioactivity with EC50 values of 0.52–25.31 µg mL−1 toward three typical phytopathogens. Moreover, the assembly of the supramolecular binary complex 3a@β‐CD is successfully elucidated and displays exceptional inhibitory activity on biofilm formation. Of note, this supramolecular binary complex significantly improves the water solubility, foliar surface wettability, and shows marked light‐responsive properties. In vivo anti‐Xoo assays reveal that 3a@β‐CD has excellent control efficiency (protective activity: 51.22%, curative activity: 48.37%) against rice bacterial blight pathogens, and their control efficiency can be elevated to values of 55.84% (protective activity) and 52.05% (curative activity) by UV–vis exposure. In addition, the 3a@β‐CD are non‐toxic toward various non‐target organisms. This study therefore offers new insights into the potential of host‐guest complexes as a feasible pesticide discovery strategy characterized by a safe, biocompatible, light‐responsive release, and antibiofilm properties for overcoming intractable plant bacterial diseases.