To avoid the complex core surface functionalization or pretreatment that is necessary in order to coat latex and silica colloids with a uniform, complete metal shell, the solvent‐assisted route has been explored to prepare a complete metal (Ag or Au) shell with controlled thickness on polystyrene (PS) colloids and the electroless plating approach, based on electrostatic attraction, has been explored to prepare a complete silver shell with controlled thickness on silica colloids. Without any additional surface treatment, the as‐prepared complex core–shell colloids can be crystallized directly into long‐range‐ordered structures with photonic bandgaps, as reported here for the first time. These ordered structures may find potential applications as substrates or physical systems for the enhancement of Raman scattering studies, besides applications as photonic crystals. The optical plasmon resonance of the composite core–shell colloids changes with metal shell thickness, the wavelength varying over hundreds of nanometers. Our coating routes are facile and versatile, and can be extended to coat PS and silica colloids with any other metal whose ion or complex can be reduced in solution.