Thermal stability and phase homogeneity of the triphylite LiFePO4 compound were investigated by means of Raman spectroscopy. A detailed check of phase homogeneity of undoped samples obtained from different preparation routes—hydrothermal, sol–gel, and solid state synthesis—and Mn-doped compounds from solid-state synthesis was performed by means of a mapping of the Raman spectra. The triphylite compositional and structural properties were carefully investigated also with the help of structural refinements and magnetic techniques, which also allowed us to reveal and identify the impurity phases formed together with the olivine LiFePO4. The effect of laser irradiation on the triphylite thermal stability was thoroughly investigated and related to the synthesis route, to the doping, and to the sample homogeneity. The thermal stability of iron oxides, present both as synthesis products and as consequence of the irradiation itself, was also analyzed following the magnetite→maghemite→hematite phase transformation. All the experimental observations concur in indicating that the effectiveness of the laser heating on these compounds mainly depends on grain size and the degree of order of the olivine structure, the highest thermal stability being displayed in the case of the nonhomogenous undoped samples obtained from solid-state preparation, which show a highly ordered triphylite phase. Copyright © 2010 John Wiley & Sons, Ltd.