Pesticide spraying on superhydrophobic wheat leaves suffers from severe spray loss and off-target effects, leading to extremely low efficient utilization and serious ecological pollution. Herein, inspired by the wet adhesion properties of mussel foot proteins, a biomimetic pillar[5]arene-based supramolecular coacervate (PSC) is developed through supramolecular self-assembly driven by host–guest interactions between amino pillar[5]arene and sodium laurate. The resulting PSC exhibits high surface activity, low shear viscosity, and 3D network-like micro-nanostructures, endowing PSC with strong affinity and adhesion to wheat leaves' micro-nanostructured surface. During high-speed liquid-solid impact, the network-like microstructures of PSC tightly entangle and bond with the micro-nanostructures of wheat leaves by structure-matching principles to achieve complete deposition and good wetting on wheat leaves tilted with different angles, remarkably improving agrichemical utilization. After even exposure to rainwash erosion, PSC possesses excellent deposition and adhesion behaviors. In actual spraying application, PSC combined with tebuconazole synergistically increases the effective deposition rate of tebuconazole to 57.82% on wheat leaves tilted at 60°, representing a 3.5 fold increase compared to commercial suspensions, exhibiting excellent control efficacy against Rhizoctonia solani with 91.15% inhibition effects. This work provides highly effective avenues for constructing an eco-friendly supramolecular pesticide formulation, which is of great significance for achieving decrement and synergism of agrichemicals.