The design and performance of a cooled sample introduction probe for fast atom bombardment or other liquid secondary ionization mass spectrometric studies are described. Cooling relatively volatile matrix materials (sulfolane, thioglycerol, and tetraglyme, for example) in situ in the ion source can increase the duration of the sample spectrum by a factor of 10. Cooling also permits a much wider range of matrix materials to be used. As an example, the spectrum of the carbohydrate, peracetyl [Glu(β1 → 3)] 7 Glucitol in tetraglyme matrix, is shown to give an excellent spectrum including cleavage peaks corresponding to losses of the first five sugar residues. The spectrum lasted approximately 10 times longer when the probe tip was cooled to 9 ± 1°C than when no cooling was used, corresponding to a 10-fold increase in integrated sensitivity.