AbstractWithout overnight heating and stirring, Li1.2V3O8 and its analogs Li1.2‐yNayV3O8 (0 ≤ y ≤ 1.2) were successfully synthesized by adding mixed solution of LiOH and NaVO3 to V2O5 gel and dehydrating the prepared gel in 150–350°C. The simplicity awards this synthesis process superiority over other low temperature synthesis routes when mass production is concerned. TG‐DTA, XRD and TEM experiments were carried out for physical characterization. By galvanostatic charge‐discharge and cyclic voltammetry tests, these products showed better electrochemical performance than high temperature products as cathode active materials in secondary lithium batteries. After treatment of Li1.2V3O8 at 250°C, it exhibited a capacity of 350 mAh/g when cycled at current rate of about 60 mA/g over the voltage range of 3.8–1.7 V vs. Li+/Li. The influence of partial substitution of Li by Na was also extensively studied.