Ion mobility spectrometry (IMS) was explored in the selective detection of nitrobenzene compounds in industrial waste water and surface water, and the selectivity was theoretically elucidated with the transformation energy in the product ion formation reaction. A linear detection range of 0.5-50 ppm and a limit of detection (LOD) of 0.1 ppm were found for 2,4,6-trinitrotoluene (TNT). With the IMS as the detection system of molecularly imprinted polymer (MIP) separation technique, the MIP-IMS system was proved to be excellent method to detect trace amount of nitrobenzene compounds in surface water, in which more than 87% of nitrobenzene compounds could be adsorbed on MIPs with 90-105% of recovery. (C) 2014 Elsevier B.V. All rights reserved.