A comprehensive review of the chemistry of polyhedral cluster complexes in whichs,p,d, andf-block metals are incorporated into C2B4-carborane cages to form the respective metallacarboranes is presented. The main focus of the review is directed toward systematizing the chemistry of metallacarboranes in order to promote their use as possible electronic, ceramic, and/or catalytic materials in addition to providing information on which we can test and expand our knowledge about the fundamental interactions that are at work in determining the structures and properties of these cluster complexes.