Templated from sacrificial colloidal assemblies, inverse opals are comprised of an interconnected periodic network of pores, forming a photonic crystal. They are used in a variety of applications, most of which, especially those in optics and photocatalysis, require a high degree of control over the long-range order, composition and refractive index. It has been shown that hybrid materials combining different components can yield materials with properties that are superior to the individual components. Here, we describe the assembly of hybrid titania/silica inverse opals using sol–gel chemistry, resulting in a mixed oxide with well-dispersed titanium and silicon. Titania has a high refractive index (2.4–2.9), but cracks typically form in the inverse opal structure; conversely, silica can produce highly ordered crack-free inverse opals, but it has a lower refractive index (∼1.4). By adjusting the ratio of titania and silica, the refractive index can be tailored while minimizing the crack density and maintaining structural order, allowing for control over the optical properties of this hybrid nanoporous material.