Herein, a new two‐dimensional (2D) Ce‐organic frameworks (referred to as SLX‐4) was achieved by traditional solvothermal conditions. Initial studies of SLX‐4 toward Hantzsch reaction showed that good catalytic activity can be obtained under mild conditions, giving the desired 1,4‐dihydropyridines in moderate to high yields. The catalyst could be reused at least 4 times keeping good catalytic activity. Moreover, compared to the previously reported MOFs catalysts for Hantzsch reactions, SLX‐4 was stable in most acidic and basic environment, and gave comparable yield.