AbstractDeposition of high‐speed droplets on inverted surfaces is important to many fundamental scientific principles and technological applications. For example, in pesticide spraying to target pests and diseases emerging on abaxial side of leaves, the downward rebound and gravity of the droplets make the deposition exceedingly difficult on hydrophobic/superhydrophobic leaf underside, causing serious pesticide waste and environmental pollution. Here, a series of bile salt/cationic surfactant coacervates are developed to attain efficient deposition on the inverted surfaces of diverse hydrophobic/superhydrophobic characteristics. The coacervates have abundant nanoscale hydrophilic/hydrophobic domains and intrinsic network‐like microstructures, which endow them with efficient encapsulation of various solutes and strong adhesion to surface micro/nanostructures. Thus, the coacervates with low viscosity achieve high‐efficient deposition on superhydrophobic abaxial‐side of tomato leaves and inverted artificial surfaces with a water contact angle from 170° to 124°, much better than that of commercial agricultural adjuvants. Intriguingly, the compactness of network‐like structures dominantly controls adhesion force and deposition efficiency, and the most crowded one leads to the most efficient deposition. The tunable coacervates can help comprehensively understand the complex dynamic deposition, and provide innovative carriers for depositing sprayed pesticides on abaxial and adaxial sides of leaves, thereby potentially reducing pesticide use and promoting sustainable agriculture.