In view of the interesting structural features and suitability of heterometallic alkoxides (supported by chelating ligands) as precursors for oxide-ceramic materials, studies have been recently extended to novel types of heterometallic alkoxides derived from various polyols. These are generally obtained by the interactions of residual hydroxy groups in the homometallic derivatives with alkoxides of other metals.In this review, the synthesis and characterization (including X-ray-based structures) of these novel heterometallic coordination systems with polyols (glycols, di- and tri-ethanolamines (teaH 3 )), derived from the corresponding homometallic species, have been reviewed with a full list of compounds described till 2002.