Well-defined heterobi- and heteropolymetallic alkoxides are valuable precursors for numerous oxide materials with great application potential. Simple and high yield synthetic routes to such compounds are always highly desirable. This Perspective describes one of the methods that utilizes, as starting materials, homoleptic monometallic alkoxides with a free alcoholic moiety coordinated to the metal. The moiety constitutes a convenient anchor for upcoming organometallics.