ABSTRACTIn this study, we prepared a porous poly(methyl methacrylate) (PMMA) film on an Si surface with a novel dipping method. We conducted the process by directly dipping the Si substrate into acidic aqueous media in a simple flask at 10 °C. First, 4‐nitrobenzene diazonium tetrafluoroborate (NBD) was spontaneously reduced at the Si surface. Then, the aryl radicals during the reduction of NBD were directly grafted onto the Si surface. Meanwhile, the aryl radicals initiated the polymerization of methyl methacrylate (MMA) monomers, and the radical‐terminated PMMA chains formed in the solution were grafted onto the Si surface. Because water was a poor solvent for MMA, the grafted PMMA chains easily aggregated together, and this resulted in a porous polymer film. The porosity of the film depended on the grafting time and the MMA concentration. Furthermore, the permittivity of the porous PMMA film was relatively low, and its dielectric dissipation factor was extremely small. Therefore, its excellent dielectric properties should allow the porous film to have many applications in industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44930.