The first direct ion exchange of a luminescent metal complex into an alpha-zirconium phosphate framework has been accomplished. A hydrated form of alpha-ZrP, with an expanded 10.3 Angstrom interlayer distance, has been used for the intercalation of Ru(bpy)(3)(2+), resulting in further expansion to 15.2 Angstrom. The Ru(bpy)(3)(2+) luminescence band is slightly blue-shifted. High Ru(bpy)(3)(2+) loadings lead to luminescence self-quenching.