The first large‐pore, mixed‐valent titanium phosphate was hydrothermally synthesized by using elemental titanium as a starting material, and 1,3‐diaminopropane as a template. The structure displays an open framework containing octahedrally coordinated TiIII and TiIV centers and tetrahedrally coordinated P centers; the diamine molecules are located within the zigzag channels (the picture shows a polyhedral representation of the structure).