The discovery of carborane-siloxane polymers in the early 1960's furnished a promising lead in the search for hlgh-temperature performance properties. However, the pioneering processes for carborane and carborane-siloxane synthesis Involved difficult procedures and/or low efficiencies. This severely limited not only the large-scale preparation of carboranes and linear carborane-siloxane polymers but also effectively eliminated the preparation of carboranes in the research laboratory. Thus a need existed for processes which overcame these difficulties and which would allow for the full exploitation of these materials. This review describes the development of a second generation of technology which makes carboranes and linear carborane-siloxanes readily available for the first time.