A high intensity bluish-white emitting Ba2TiP2O9 phosphor was synthesized by a conventional solid-state reaction method and the precise crystal structure was investigated for the first time by Rietveld refinement analysis. Ba2TiP2O9 has a monoclinic crystal structure with a space group C2/c (no. 15), which is built out of PO4 tetrahedra and TiO5 pyramidal polyhedra connected to form a chain structure along the c-axis. The emission of Ba2TiP2O9 is due to a charge transfer transition between Ti(4+)-O(2-) in the pyramidal TiO5. The obtained Ba2TiP2O9 was excited efficiently by UV and VUV and displayed a bright bluish-white luminescence.