Polyaniline is a model molecular system in the study of conductive polymers. Ionic liquids, on the other hand, are becoming more and more a very convenient alternative for conventional organic solvents. The dissolution of polyaniline-emeraldine base (PANI-EB) in imidazolium ILs leads to its doping, as indicated by optical and resonance Raman spectroscopies. In this study, it is proposed that the interaction of PANI-EB and imidazolium ILs involves the specific interaction of the quinoid moiety of the former with the imidazolium ring of the latter, an interpretation that is also based on N K-edge XANES measurements of neat PANI-EB, neat ILs, and of their solutions.