AbstractThe detailed shape of the dense material network of inverse opals has a significant influence on the appearance of band gaps in these photonic crystals. One example of these topologically very similar networks is the skeleton structure, which can show two complete band gaps. Like all inverse opals, these structures are self‐standing and can be fabricated via self‐assembly strategies. The first step for obtaining these novel kind of photonic crystals has been achieved by synthesizing a titania skeleton structure.