The increasing number of applications for fast atom bombardment (FAB) mass spectrometry has seen a corresponding increase in the use of different matrix compounds. This review discusses briefly the use of matrix compounds in general and the use of cosolvents and/or additives with glycerol that assist in producing superior FAB mass spectra than when glycerol is used on its own. The main part of the review deals with alternative matrix compounds to glycerol including thioglycerol, polyethyleneglycols, triethanolamine, diamylphenol, crown ethers and various miscellaneous matrix compounds.