Particle (monolayer) assembly is essential to various scientific and industrial applications, such as the fabrication of photonic crystals, optical sensors, and surface coatings. Several methods, including rubbing, have been developed for this purpose. Here, we report on the serendipitous observation that microparticles preferentially partition onto the fluorocarbon-coated parts of patterned silicon and borosilicate glass wafers when rubbed with poly(dimethylsiloxane) slabs. To explore the extent of this effect, we varied the geometry of the pattern, the substrate material, the ambient humidity, and the material and size of the particles. Partitioning coefficients amounted up to a factor of 12 on silicon wafers and even ran in the 100s on borosilicate glass wafers at zero humidity. Using Kelvin probe force microscopy, the observations can be explained by triboelectrification, inducing a strong electrostatic attraction between the particles and the fluorocarbon zones, while the interaction with the noncoated zones is insignificant or even weakly repulsive.