Time-consuming investigation of rhizodeposit composition by leaching, freeze-drying of leachate, and pyrolysis-field ionization mass spectrometry (Py-FIMS) of solid samples was replaced by direct Py-FIMS of a 5 microL liquid rhizodeposit sample which was evaporated overnight in the quartz tube of a mass spectrometer inlet system. Application of this new rapid technique to a set of 14 liquid rhizodeposit samples from maize (Zea mays L.), leached twice with a time lag of 80 min, unequivocally showed the effect of soil texture on the chemical composition of the rhizodeposits. Irrespective of leaching time, a partial least-squares analysis separated the Py-FI mass spectra of the maize rhizodeposits leached from a soil from those leached from a soil + quartz sand-mixture (prepared by addition of 50% w/w quartz sand to the original soil). The signals which had the strongest discrimination power and were significantly enriched in leachates from the soil + quartz sand were assigned to sugars, peptides and polyamines. Mass signals of putrescine and cadaverine, a priori not expected in the rhizodeposits, were indicators of modified root environment and rhizosphere processes in the soil + quartz sand. In conclusion, the new rapid mass spectrometric profiling method is suitable for rhizosphere research because it requires very small sample volumes, is fast and highly sensitive to detect and quantify a wide range of a priori expected and unexpected organic substances.