Integration of luminescent rare earth ions and iridescence into a zirconium oxide photonic material is attractive for the design of new optical devices. The free-standing chiral nematic mesoporous films of ZrO₂:Eu³⁺ are assembled by a hard-templating approach using nanocrystalline cellulose-templated silica. The ZrO₂:Eu³⁺ films show tunable optical properties. The chiral nematic structured ZrO₂:Eu³⁺ exhibits selective suppression of the spontaneous emission of Eu³⁺ and the capability to modulate the lifetime of luminescent Eu³⁺.