Li-Ti-O (abbreviated as LTO) nano-composites were synthesized via sol-gel process, and then doped BaTiO3 based X7R type ceramics. The LTO nano-composites and their ceramics were characterized by means of thermaogravimetric, Fourier-transform infrared, X-ray diffraction methods, transmission electron microscopy. We also characterized the dielectric properties of the LTO doped BaTiO3 based ceramics of X7R type. The results indicated that LTO nano-composites were nanometer scale powders. The pH value and calcining temperature had an influence on particle size of LTO sintering aids. At pH about 3 and with calcining at 600 °C, the nano-composites attained minimum particle size (about 10 nm). By adding 0.10 wt% of the LTO nano-composites, the temperature permittivity achieved about 4200 when sintered at 1240 °C for 4 h, and the dielectric properties met X7R standard.