Photonic crystals fabricated from the colloidal spheres of polymethyl methacrylate (PMMA) using the inward-growing self-assembly technique were subse-quently in-filled with zinc oxide (ZnO) prepared by the sol–gel process. The polymer template was removed by heat treatment and chemical method to get ZnO-inverse photonic crystal. The structural quality of the inverse photonic crystal obtained by the chemical method was found to be superior to that obtained by heat treatment. The ZnO-inverse photonic crystal obtained by the chemical method was further treated at an elevated temperature to ensure the crystalline nature of ZnO. Laser-induced emission tudies on ZnO-inverse photonic crystals were carried out at an excitation wavelength of 325 nm. The emission spectra showing UV and visible bands at collection angle of 45° from the direction of excitation helped to establish the role of crystalline ZnO.