The structure, lithium ion conductivity and reaction suppression against lithium of the novel xLaAlO3–(1− x)La0.57Li0.30TiO3 oxides (0≤ x ≤1) with a perovskite related structure (ABO3) are studied by using X-ray diffraction, ac impedance and digital multimeter. The results show that owing to the geometric environment, consisting of La3+, Li+ and vacancy at A-sites, the conductivities from x =0 to 20mol% are maintained in the range of 10−4 Scm−1, and decrease to 8.92×10−9 Scm−1 with 30–40mol% LaAlO3 addition. When the value of x is larger than 50mol%, the corresponding oxides no longer have the characteristic of ionic conduction. A stable solid electrolyte is also observed to alleviate the reaction significantly when the incorporated LaAlO3 content is 40mol%.