Isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) form a stereocomplex using an inkjet system. As compared with conventional methods such as simply mixing solutions or dipping substrates with a layer-by-layer (LbL) approach, a much smaller amount of polymer chains (9.0 × 107) can theoretically associate with each other, and the process is quicker. Glass and polystyrene substrates are compared as substrates, suggesting different morphologies due to the solvent interactions during the rapid evaporation. The stereocomplex structure is confirmed by infrared spectroscopy and X-ray diffraction.