PMMA microsphere arrays are fabricated by a double replicating method with common used polystyrene colloidal crystal template. High quality ZnO inverse opals formed by electrodeposition play the key role between the PMMA microsphere arrays and polystyrene colloidal crystals. The electrodeposition method has advantage on fabricating IO structures with high solid fraction. After the subsequently in-situ polymerization of MMA in the voids of ZnO inverse opals, the ZnO is removed by hydrochloric acid solution. Microsphere arrays fabricated by PMMA or PMMA doped with Alq 3 are prepared. Reflection stop bands are detected from the formed PMMA microsphere arrays. Solid fraction from 37% to 50% of the PMMA arrays can be formed by different in-situ polymerization modes of MMA. The photoluminescence of Alq 3 in the PMMA spheres is partly suppressed at the wavelength of the photonic stop band induced by PMMA arrays.