Here we present a new family of MOF-crystalline inorganic glass composites (MOF-CIGCs) combining a Ti-MOF (MIL-125-NH2) and a phosphate-based glass (70%P2O5-20%Na2O-10%Na2SO4). The atomic interfacial interactions between phases were unveiled by X-ray total scattering analysis using the pair distribution function (PDF) and the photocatalytic activity of this materials family was evaluated and compared with the pristine MOF.