Opal-inverse opal interlocked composites consisting of opals of hollow spheres with window channels interlocked, have displayed new properties. A facile and general method has been reported to synthesize the ordered composites. Polymer shells are first grown onto the surface of a silica sphere of an opal template by ATRP, which is followed by a sequential modification of the shells resulting in functional groups. Composite shells are favorably synthesized within the functional polymer shells. After the removal of silica opal templates, opal-inverse opal interlocked structures with varied compositions of polymers, inorganic materials, and carbon are achieved.