In present paper a new niobate materials Ba5LixTixNb10-xO30 were synthesized by doping Li+ in the system BaO- TiO2- Nb2O5 in millimeter wave field. X-ray diffraction (XRD) quantitative and scanning transition spectroscopy (SEM) analysis were employed to study crystal structure and microstructure of reaction products. It was found that pure products could be obtained at temperature 900, 8 min which is lower comparing with that by conventional method. The XRD data shown the crystal belongs to tetragonal tungsten bronze structure with space group P4bm. The grain size synthesized in millimeter wave field had smaller size, narrower distribution, better sinter-ability, and without hard agglomeration comparing whit that obtaining from conventional synthesis. At lower temperature Ba5LiTiNb9O30 is a tetragonal ferroelectric phase.