We describe the preparation and characterization of photonic colloidal crystals from silica spheres with incorporated luminescent [Mo₆Br₁₄]²⁻ cluster units. These structures exhibit strong angle-dependent luminescent properties. The incorporation of one or several planar defects in the periodic structures gives rise to the creation of a passband in the stopband. In the energy range of this passband, an increase of the emission intensity has been found.