Polymer monoliths were prepared in capillary format (250 mm i.d.) and used as solid supports for the immobilisation of the conducting polymer polyaniline (PANI). The immobilisation of PANI was confirmed on the large macro-porous structure of a polystyrene–divinylbenzene (PS-co-DVB) monolith. The surface coverage of polyaniline was characterised by field emission scanning electron microscopy (FESEM) and by capacitively coupled contactless conductivity detection (C4D), which was operated in scanning mode to non-invasively visualise the axial distribution of the immobilised PANI and to provide information on its doping state. To further demonstrate the successful functionalisation of the monoliths, the PANI-functionalised monoliths were demonstrated as switchable, weak anion-exchange stationary phases as confirmed by studying the retention of iodide using a perchlorate eluent.