The use of poly(vinyl acetate) (PVAc) nanogels for the fabrication of patterned porous surfaces is described. These nanogels were synthesized by controlled radical cross-linking copolymerization (CRCC) involving a xanthate-mediated reversible addition fragmentation chain transfer (RAFT) mechanism. This synthesis methodology allowed for the preparation of nanogels based on PVAc with a controlled constitutive chain length and average numbers of chains and cross-links. Solutions of these branched polymers were prepared in THF with a fixed amount of water and spin coated onto a surface of graphite. The surface porosity of corresponding films was observed by atomic force microscopy (AFM). Compared with linear PVAc homologues with a degree of polymerization (DP) sufficiently high to favor the formation of porous structures (DP = 50), a sharper and better defined porosity was observed with nanogels, the constitutive chains of which had the same DP. For nanogels differing only in their cross-link density, the pores were smaller and better defined in the case of the higher cross-link density, suggesting an enhanced stabilization of the water droplets during film formation. To explain these observations, it is postulated that: PVAc nanogels can behave as compact particles providing steric stabilization of water droplets, which is referred to as a Pickering effect. The coalescence of water droplets would be better prevented as the cross-link density of the nanogels increases, resulting in a smaller size pore.