Pesticide spraying serves as a prevalent segment in crop production for substantial economic and ecological benefits. Nevertheless, the existing pesticide formulations are often plagued by droplets rebounding during the spraying process, and the controlled-release, photolysis protection, and non-targeted bio-friendliness are not inadequately considered. Herein, by combining spinosad (SSD, a model pesticide) with glycyrrhizic acid (GL) as an attractive building block, a supramolecular co-assembly strategy is employed to elaborate pesticide formulations (GL-SSD) simultaneously featuring high deposition, controlled-release, and environmental friendliness. The resulting spherical GL-SSD nanoparticles (NPs) have an average diameter of 207 nm and show an improved 5.2-fold photostability compared with commercial spinosad suspension (SSD SC). Upon impacting on hydrophobic surfaces of polytetrafluoroethylene film and cabbage leaf, the droplets of GL-SSD NPs exhibit superior affinity to the micro/nano structure of the surface. Consequently, the droplet rebounding is inhibited effectively, ensuring high deposition efficiency of droplets on surfaces. In addition, the release of SSD from GL-SSD NPs can be controlled by pH variation. Indoor toxicity and pot experiments demonstrate that GL-SSD NPs possess good control efficacy against Plutella xylostella. The work offers an alternative approach for the development of multi-functional and sustainable pesticide formulations with promising potentials in actual agriculture production.