The thermal transformations of gamma-titanium phosphate, Ti(PO4)(H2PO4)center dot 2H(2)O, have been studied by thermal analyses (thermogravimetry (TG) and differential thermal analysis (DTA)) and variable-temperature P-31 magic-angle spinning (MAS)/CPMAS and 2D P-31-P-31 spin-exchange NMR. The structure of this material has been refined from synchrotron powder X-ray diffraction data (monoclinic, P2(1), a=5.1811(2) angstrom, b=6.3479(2) angstrom, c=23.725(2) angstrom, beta = 102.57(1)degrees). Vyazovkin's model-free kinetic algorithms have been applied to determine the apparent activation energy to both dehydration and dehydroxylation of gamma-titanium phosphate. In these processes, several overlapped steps have been detected. Structural models for Ti(PO4)(H2PO4)center dot H2O and Ti(PO4)(H2P2O7)(0.5) intermediate layered phases have been proposed.