Electronic thin films play a ubiquitous role in microelectronic devices and especially hold great promise for flexible electronics, energy conversion and storage, and biomedical applications. Their characterizations, including ultra‐thin, large‐scale dimensions, stretchability, and conformal ability to curved or 3D structures, present new challenges for thin film fabrication based on the solution method. Electrospray deposition emerges as a feasible method for fabricating large‐area, flexible, and curved films. It offers many advantages such as material adaptability, controlled atomization, tunable film morphology, and shape retention on complex substrates. These advantages make it a key method for fabricating high‐performance films on large‐area, 3D surfaces. This work presents a comprehensive review of the mechanisms, processes, applications, and equipment of electrospray deposition. First, the fundamental principles of electrospray deposition are introduced, focusing on the mechanisms and scaling laws of liquid atomization. Moreover, the control methods for electrospray modes, structures, and film morphology are discussed. These advanced control methods pave the way for the fabrication of smart skins, wearable devices, and energy conversion and storage components. Finally, this work introduces three types of electrospray deposition manufacturing equipment to illustrate the advantages of electrospray deposition for large‐area, and 3D surface manufacturing.