Methods for the crystal structure determination from powder diffraction data are reviewed with special emphasis on the application to technical ceramics. Experimental techniques using other than laboratory X-ray, such as synchrotron radiation, neutron and electron beams, are also described. As an illustrative example, the crystal structure determinations of compounds LaNbTiO6, La0.462Nb0.614Ti0.386O3 and La0.37Nb0.889Ti0.111O3 in the ternary system of La2O3–Nb2O5–TiO2 are reported