Hollow polymer nanoparticles are of great importance in various industrial fields such as drug delivery vehicles in pharmaceutics, high thermal insulation materials for heat flow blocking and energy savings, and materials with unique optical properties. While the fabrication methods for hollow polymer nanoparticles have been studied and developed by numerous researchers, most synthesis methods require a rather complicated process, including a thorough core-washing step to formulate pores inside the particles. Single-step synthesis methods were developed to overcome this practical issue by utilizing the sacrificial solvent filling the pores temporarily and having it naturally evaporate without further process; however, such processes could not produce sub-200 nm diameter particles, which limit the application for high surface area applications. Herein, we have developed an innovative synthesis method that can overcome the particle size limitation by utilizing a sacrificial solvent for pore formation and a recondensation inhibitor. Pseudo-state Ostwald ripening was realized by selecting the sacrificial solvent with less affinity to the copolymer of hollow polymer particles, thus inhibiting the particle growth during polymerization. We have successfully obtained 120 nm diameter hollow PS-PMMA copolymer particles in large quantity via the single-step preparation of emulsion polymerization.