A combination of an alternating layer-by-layer assembly of isotactic (it) and syndiotactic (st) poly(methyl methacrylate) (PMMA) and supramolecular cyclodextrin microcubes as a template core forms hollow microcubes composed of it-/st-PMMA stereocomplex films. Simply washing with water removes the cyclodextrin templates from the it-/st-PMMA stereocomplex film-coated particles to give hollow microcubes.