Ion mobility spectrometry (IMS) with handheld and transportable devices permits the sensitive detection of chlorinated compounds which are important in environmental monitoring. The ion mobility spectra in negative measuring modus mostly show one product ion peak [(H(2)O)(n)Cl(-)] due to dissociative electron attachments. In this paper, we investigated relevant chlorinated compounds (R-Cl) where R represents allyl-, benzyl-, phenyl-, alkyl- and vinyl-groups. These groups cause differences in the R-Cl bond strength and differences in the cleavage of chlorine can therefore be expected. All chlorinated substances investigated provide the same product ion peak at 2.75 cm(2)Vs(-1) independent on the different C-Cl bond strength. However, distinct influences of structural features on the peak intensities of the (H(2)O)(n)Cl(-) product ion peak were established. Generally, increasing sensitivities were obtained in the order chlorobenzenes