A high-nuclear Mn 72 W 48 cluster has been successfully synthesized by employing acetate coordinated Mn12 and Na2WO4 as starting materials. To investigate the synthesis mechanism, a series of synthesis experiments and high-resolution ESI-MS tests were designed and conducted. These experimental results demonstrate that inorganic tungstates exhibit better coordination capacity and variability than organic acetates in Mn 12 . Furthermore, a series of low nuclearity Mn clusters and Mn–W species were successfully detected and a possible synthesis mechanism of Mn 72 W 48 was proposed. These results show that inorganic tungstate ligands have a great potential to construct high-nuclear transition-metal-oxo clusters by forming various intermediates.