The formation of multilayered inverse opal photonic crystals by atomic layer deposition has been investigated, and shown to provide a flexible and precise technique to control the properties of photonic crystals. Inverse opals were formed by infiltration of SiO2 opal templates with conformal layers of ZnS:Mn and TiO2, followed by etching. The optical properties were further tuned by backfilling the structures with TiO2. The high-order band structure and its influence on the photoluminescent properties were studied and modification of the Cl− and Mn2+ emission peaks at 460 and 585 nm were demonstrated, respectively.