In this work we present an Atmospheric Pressure Chemical Ionisation (APCI) study of several organic solvents (methanol, ethanol, propan-2-ol, acetone, ethyl acetate, diethylamine) using the Ion Mobility Spectrometry (IMS) combined with the orthogonal acceleration Time Of Flight Mass Spectrometry (IMS-oaTOF MS). The ions were formed in interactions of the Reactant Ions (RI -H + .(H2O)3,4) with the studied volatile organic compounds (VOC's). The ions were analysed by IMS and in by IMS-oaTOF to assign ions according to their m/z to the ion mobility peaks. IMS spectra of methanol, ethanol, propan-2-ol and diethylamine exhibited only one peak (reduced ion mobilities of 2.19, 2.07, 1.98, 2.06 cm 2 .s -1 .V -1 respectively) whereas acetone and ethyl acetate were characterised by two peaks (2.15, 1.85 and 1.94, 1.53 cm 2 .s -1 .V -1 respectively). The IMS-oaTOF spectrometry assigned IMS peaks of VOC's to M . H + (H2O)n . n=0,1, 2 or M2 . H + ions, where M represent the solvent molecule.