The He I and He II spectra of 3-haloanilines were measured and assigned using a composite-molecule model. The assignments establish the relative ordering of the π IEs (associated with the benzene moiety) and those associated with the nitrogen and in-plane halogen lone-pairs. These assignments are substantiated by comparisons of He I and He II cross-section ratios, ab initio calculations using the HF-6-31G * * model, linear correlations of the in-plane lone-pairs on the halogen substituent and Allred electronegativities for the halobenzenes and haloanilines. Comparisons with the ultraviolet photoelectron spectra of 2- and 4-haloanilines also reinforce these assignments.