Colloidal photonic crystals have attracted much attention of the scientific world due to their unique optical properties and potential applications in sensing, displays, optoelectronics, controlled superwetting and other fields. Here we report the fabrication of spherical colloidal photonic crystals featured with well-ordered nanopatterns from silica nanoparticles (SiO2NPs) and gold nanoparticles (AuNPs) through a droplet-based microfluidic approach. The colloidal crystals show both the photonic band gaps (PBG) and surface plasmonic resonance (SPR) properties. These proposed hierarchically composite ‘superballs’ will have an excellent performance in sensing applications, due to the fast response (the scattering color change) to the dielectric properties of the surrounding medium. A robust and efficient strategy is proposed and demonstrated to fabricate the composite superballs with multifunctional properties, broadening the perspective of their applications by the advantages of precise control over the size of the particles and flexible change of the fluid composition.