We report a facile air-controlled electrospray method to directly deposit binder-free active materials/graphene oxide (GO) onto current collectors. This method is inspired from an electrospinning process, and possesses all the advantages that electrospinning has such as low cost, easy scaling up, and simultaneous solvent evaporation during the spraying process. Moreover, the spray slurry is only a simple mixture of active materials and GO suspension in water, no binder polymer, organic solvent, and conductive carbon required. In our research, high-capacity Si nanoparticles (Si NP, 70-100 nm) and SiO microparticles (SiO MP, 3-10 μm) were selected to demonstrate the capability of this method to accommodate particles with different sizes. Their mixture with GO was sprayed onto a collector and then thermally annealed in an inert gas to obtain Si NP or SiO MP/reduced graphene oxide (RGO) binder-free electrodes. We are also able to directly deposit fairly large electrode sheets (e.g., 12 × 21 in.) upon the application requirement. To the best of our knowledge, this is the simplest approach to produce Si-related materials/RGO layered structures directly on current collector with controllable area and loading. Si and SiO MP/RGO are evaluated in both half and full lithium cells, showing good electrochemical performance. Prelithiation is also studied and gives a high first cycle Coulombic efficiency. In addition to Si-related materials, other materials with different shapes and sizes (e.g., MoO nanobelts, Sn/carbon nanofibers, and commercial sulfur particles) can also be sprayed. Beyond the preparation of battery electrodes, this approach can also be applied for other types of electrode preparation such as that of a supercapacitor, fuel cell, and solar cell.