A novel multiscale porous architecture where an individual particle is nested inside a hollow chamber of inverse-opal (IO) frame is created using a large scale self-assembly of core-shell structured colloidal particles and subsequent selective removal of the outer shells of the colloids. Since the nested particle is smaller than the size of individual IO chamber, the interconnected nanochannels are spontaneously formed within the structured frame. The size of internal nanochannels is readily tuned to have high permeability and size-selective separation capability, which is successfully tested for nanoparticle separation.