Abstract A facile and low-cost method was developed to synthesize a series of novel heterogeneous catalysts from cyclodextrins and Mg or Zn of salts. These catalysts were demonstrated to be efficient for converting sustainable plant oils to biodiesel under mild conditions (ambient pressure, 65 °C). Mechanistic studies indicated that the excellent performance of the catalysts could be attributed to their unique structural characteristics, wherein both the metal ions and the cyclodextrin units worked cooperatively for synergistic activations of substrates.