Negative-ion fast atom bombardment mass spectra of hypervalent germanates, silicates and titanate with the use of two matrices, glycerol and m-nitrobenzyl alcohol, were studied. In the case of germanates a complete reaction of the studied anion with glycerol is observed, so it is impossible to use such a matrix to identify these compounds. The use of m-nitrobenzyl alcohol allows spectra to be obtained that are significant with respect to the structure for all the studied compounds. However, for each compound a partial reaction of this matrix is observed. Further, in the case of doubly charged anions, the adduct ion obtained with an alkali metal cation does not show glycerol reactivity whereas such reactivity occurs from the adduct ion obtained with proton.