A simple and effective approach for the preparation of the solid superbasic La2O3–SBA‐15‐supported KF (KF/La2O3–SBA‐15) was developed by a low‐temperature strategy. The KF/La2O3–SBA‐15 with ordered mesostructure and a high base strength (H−=27.0) was realized at 350 °C in still air, which breaks the traditional method of thermally induced decomposition of basic metal nitrate derived species KNO3 under higher temperatures (>600 °C). The resultant mesoporous basic materials were adopted for the production of 1‐methoxy‐2‐propanol from propylene oxide and methanol. It showed excellent catalytic performance exhibiting 93 % conversion of propylene oxide and 93 % selectivity to 1‐methoxy‐2‐propanol. This performance is better than that over the catalysts without mesoporous silica despite having a higher KF content.