Different added proportion of ZrO₂ in TC4/ZrO₂ composite thin-wall samples were produced by laser engineered net shaping. Influence of scanning speed on thermal stress in forming process was studied. X-ray diffractometer analysis(XRD), scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS) were carried out for the sample phase composition, microstructure and elements distribution respectively. The research indicates that lower scanning speed can reduce the residual stress of thin-wall samples and the tendency to cracking. The result of XRD shows that when the proportion of ZrO₂ is higher than 30%, nonstoichiometric compound ,TiO.325, is formed; The grain morphology of TC4 matrix changed from acicular, lamellar to bulk grain with the increasing of proportion of ZrO₂; The result of EDS shows a segregation of ZrO₂ at lamellar Ti grain boundaries; The content of Zr in Ti solid solution increases with the content of ZrO₂increasing.A reliable technical support is provided by this study to finally form TC4/ZrO₂ graded materials.