9-Aminoacridine was established as a matrix for the detection of neutral oligosaccharides in negative ion mode matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) mass spectrometry. Sodium iodide proved to be a useful additive inducing formation of stable iodide adducts of the analytes, in particular for oligosaccharides with a degree of polymerisation (DP) of three and higher. Lower oligomers (DP <3) and monosaccharides show more stable adducts with chloride ions. After optimisation of the sample preparation procedure, limits of quantitation were determined for alpha-cyclodextrin and cellopentaose at 7 and 13 pmol, respectively, with a linear detector response over two concentration orders. The iodide additive could be successfully employed on MALDI-TOF mass spectrometers with vacuum and atmospheric pressure ion sources. The value of the new method to solve biological problems has been demonstrated by the analysis of a mixture of beta-glucane elicitors isolated from the cell walls of Phytophthora sojae.