AbstractPolymer solar cells are attracting attention as next-generation energy sources. Scalable deposition techniques of high-quality organic films should be guaranteed to realize highly efficient polymer solar cells in large areas for commercial viability. Herein, we introduce an ultrafast, scalable, and versatile process for forming high-quality organic films on an aqueous substrate by utilizing the spontaneous spreading phenomenon. This approach provides easy control over the thickness of the films by tuning the spreading conditions, and the films can be transferred to a variety of secondary substrates. Moreover, the controlled Marangoni flow and ultrafast removal of solvent during the process cause the films to have a uniform, high-quality nanomorphology with finely separated phase domains. Polymer solar cells were fabricated from a mixture of polymer and fullerene derivatives on an aqueous substrate by using the proposed technique, and the device exhibited an excellent power conversion efficiency of 8.44 %. Furthermore, a roll-to-roll production system was proposed as an air-processable and scalable commercial process for fabricating organic devices.