Abstract Three mono‐substituted and six poly‐substituted haloalkanes derivatives were investigated by means of negative ion mass spectrometry (NIMS). Available electron transmission spectroscopy (ETS) data were used for the treatment of NIMS results. Comparison of the ETS spectra of mono‐substituted bromo‐ and chloroalkanes show that these families of compounds exhibit similar regularities in the process of NI formation. Capture of the p ‐partial wave dominates in the lowest anion state formation. In the series of mono‐substituted bromo‐ and chloroalkanes the energy difference ( Shift ) between the vertical attachment energy (VAE) in ETS spectra and the maximum of the NI formation in dissociative electron attachment (DEA) spectra correlates approximately linearly with the VAE value for the given molecule. The slopes of these dependencies are different for the mono‐substituted chloro and bromo derivatives. It is conjectured that, in the derivatives di‐substituted in the 1,2‐positions, there is a shallow minimum in the repulsive anion potential curve, which makes possible temporary trapping of the anion. This delay is long enough for the rearrangement process and formation of the Hal ions. This effect is not detected in 1,1‐halogenated derivatives. Copyright © 2006 John Wiley & Sons, Ltd.