By addition of excess acid into the reaction mixture, a series of organically-derived Anderson-type polyoxometalates, {[R1CR2(CH2O)2]CrMo6O18(OH)4}(3-), with diols as the ligands are reported herein. Such a diol functionalization mode not only works for some specific triol ligands but also can readily be extended to the diol ligands, which will greatly enrich the species of alkoxo-derivatized Anderson POM clusters.