Herein, debris particulates of nanoporous silver (np-Ag) were synthesised by a dealloying method, and their integration behaviour and surface-enhanced Raman scattering (SERS) properties during iodine functionalisation were examined. It was found that the dealloyed np-Ag debris particulates gradually assembled to form rigid nanoporous microspheres comprising Ag nano-ligaments due to mechanical collisions during iodine treatment. High-resolution transmission electron microscopy and X-ray photoelectron microscopy clearly showed the iodide surface of np-Ag, which was dotted with iodine or iodide 'nanoislands'. The exceptional, and unexpected, integration and surface structures result in a highly enhanced localised surface plasmon resonance. Furthermore, the robust nanoporous microspheres can be employed individually as as-produced miniaturised electrodes to electrically enrich target molecules at parts-per-trillion levels, so as to achieve charge selectivity and superior detectability compared with the ordinary SERS effect.