Monodispersed microspheres play a major role in optical science and engineering, providing ideal building blocks for structural color materials. However, method towards high solid content (HSC) monodispersed microspheres has remained a key hurdle. Herein, we demonstrated a facile access to harvest monodispersed microspheres based on the emulsion polymerization mechanism, where anionic and nonionic surfactants were employed to achieve the electrostatic and steric dual‐stabilization balance in a synergistic manner. Monodispersed poly(styrene‐butyl acrylate‐methacrylic acid) (P(St‐BA‐MAA)) colloidal latex with 55 wt.% HSC was achieved, which shows an enhanced self‐assembly efficiency of 280% comparing with the low solid content (10 wt.%) latex. In addition, Ag‐coated colloidal photonic crystal (Ag@CPC) coating with near‐zero refractive index is achieved, presenting the characteristics of metamaterials. And a 11‐fold photoluminescence (PL) emission enhancement of CdSe@ZnS quantum dots (QDs) is realized by the Ag@CPC metamaterial coating. Taking advantage of high assembly efficiency, easily large‐scale film‐forming of the 55 wt.% HSC microspheres latex, we could easily produce robust Ag@CPC metamaterial coatings for passive cooling. The coating demonstrates excellent thermal insulation performance with theoretical cooling power of 30.4 W/m2, providing practical significance for scalable colloidal photonic crystal (CPC) architecture coatings in passive cooling.This article is protected by copyright. All rights reserved