Polydopamine, formed by oxidation of dopamine, is a bioinspired polymer developed for multifunctional coatings by Lee et al. in 2007 by drawing inspiration from the adhesive proteins found in mussels. Due to their high versatility and substrate-independence, polydopamine coatings are gaining considerable attention in a plethora of research fields, particularly in the coating of particles, but systematic investigations of the polydopamine coating process are lacking in the literature. In this study, we explore by TEM and thermogravimetric analysis the polydopamine coating process on alumina microparticles, tungsten carbide microparticles and tungsten carbide nanoparticles. By choosing two substrates with similar size but different material (Al2O3 and WC), as well as two substrates of the same material but different size (WC micro- and nanoparticles) we investigate the effects of both substrate material and substrate size, in order to gain some insights into the polydopamine particle coating process. As opposed to what is generally assumed in the literature, we found that the polydopamine coating thicknesses on particles, as well as the thickness growing trend, depend on the particles size and material. In particular, after 24 h of polymerization time the polydopamine coatings reached a thickness of 65 ± 10 nm in the case of Al2O3 microparticles, 18 ± 4 nm in the case of WC microparticles and 33 ± 6 nm in the case ofWC nanoparticles.