PbTiO3 nanowires is produced by stainless steel reaction kettle with Teflon lined. The crystal structure of nanowire was analyzed by electron backscatter diffraction (EBSD). At present, EBSD is seldom used to analyze these powder materials with fine crystalline grain and nanosized materials. An attempt is carried out to analyze the powder materials with fine crystalline grain by EBSD. PbTiO3 nanowires is investigated by EBSD, and then analyzed by X-ray diffraction and Scanning Electron Microscopy (SEM). The crystal structure of PbTiO3 is P4mm(99), and the cell parameter is cell = 3,905 × 4,156 A. Experimental results of EBSD are accordant with that of XRD, which illuminates that surface EBSD analysis technique is feasible to determine crystal structure and orientation of powder material with new structure.