This review summarizes recent progress of the ordered macroporous composites with the opals and inverse opal structure. Synthesis and performance of the composites are emphasized. Composition of the ordered composites is tunable ranging within metal, metal alloy, metal oxide, polymer, carbon and hydrogel. The ordered structure gives brilliant color effects, which is useful for sensors and photonic crystals. The interconnected macroporous structure provides easiness for mass transportation and species culturing. This review summarizes recent progress of the ordered macroporous composites with the opals and inverse opal structures. Synthesis and performance of the composites are emphasized. Composition of the ordered composites is tunable ranging within metal, metal alloy, metal oxide, polymer, carbon and hydrogel. The ordered structure gives brilliant color effects, which is useful for sensors and photonic crystals. The interconnected macroporous structure provides easiness for mass transportation and species culturing.