Hierarchically porous titanium phosphate monoliths combining well-defined co-continuous macropores and accessible large mesopores have been synthesized for the first time via a sol-gel process accompanied by phase separation using titanium oxysulfate and phosphoric acid as precursors. The macropore size was tunable over a broad range from 0.6 mu m to 10 mu m by changing the starting composition, while the mesopore size and the specific surface area of the as-synthesized amorphous monoliths are 21 nm and 320 m(2) g (1), respectively. Crystallization of the gel network can be induced in two different ways. Calcination at elevated temperature (800 degrees C) leads to the formation of TiP2O7 and the collapse of both the macro- and meso-structures, while the solvothermal treatment of the as-synthesized gel in ethylene glycol leads to the formation of platy crystals of titanium phosphate with a layered structure at relatively low temperature. The titanium phosphate monoliths with a hierarchically porous structure are expected to be useful in various applications such as continuous-flow catalysis, water remediation and ion batteries.