The beta-Al2O3 solid electrolyte with NiO doped and Li2O stabilized is synthesized via the solid state reaction method, which is starting with α-Al2O3, Li2CO3, Na2C2O4 and Ni(NO3)2•6H2O as the raw materials. Effects of the NiO content on the mechanical and electrical performances are studied by means of thermogravimetry/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Meanwhile, the relative density, the bending strength and the electrical properties of the prepared samples are also measured in this paper. The beta-Al2O3 solid electrolyte with the appropriate amount of NiO has a higher β"-Al2O3 phase content and uniform microstructure with dense and plump grains. However, the excess NiO doping can lead the grain to molten state and make the pores become larger. It deteriorates the ionic conductivity. When the NiO content of the beta-Al2O3 solid electrolyte is 0.25wt%, the β"-Al2O3 phase