AbstractSummary: A sequential two‐step method was successfully used for the photografting of methyl methacrylate/1,2‐divinylbenzene (MMA/DVB) microemulsion onto the surface of a poly(propylene) (PP) film. Atomic force microscopy (AFM) images showed that nanoparticles with a cross‐section diameter of 60 nm were directly grafted onto the substrate's surface. Environment scanning electron microscope (ESEM) images proved that the particles formed just a single layer on the surface. The dormant groups on the nanoparticles' surface were a potential factor in the evolution of single layer into multilayer nanoparticles.The surface morphology of a PP film after being grafted with a MMA/DVB microemulsion. Nanoparticles (about 60 nm in size) are clearly tethered onto the substrate's surface with just one layer.imageThe surface morphology of a PP film after being grafted with a MMA/DVB microemulsion. Nanoparticles (about 60 nm in size) are clearly tethered onto the substrate's surface with just one layer.