Three-dimensionally ordered macroporous materials for photonic or refractory applications have been developed by an innovative approach based on mullite sol-gel infiltration of direct photonic crystals followed by burn-out and calcination. Direct photonic crystals were obtained using polystyrene spheres templates either by vertical convective self-assembly or by drop casting. The samples were then infiltrated by spin coating with mullite sol-gels prepared with two different compositions (74 wt.% Al2O3, 26 wt.% SiO2 and 80 wt.% Al2O3, 20 wt.% SiO2). The inverse opal photonic crystals prepared with both sol-gels presented a highly ordered porosity and the high-alumina composition showed stability up to 1500 degrees C. After inversion of the structure (polymeric template burn-out), the high-alumina composition showed roundness of the PS templated pores closer to an ideal sphere (empty set = 0.967) when compared to the low-alumina composition (empty set = 0.954). Although the inverse opal photonic crystals did not present a photonic bandgap, they showed structural stability at high temperatures, which enable their application as refractory materials.