The detection of ions is essential for a wide range of applications including biomedical diagnosis, and environmental monitoring among others. However, current ion sensors are based on thick sensing films (typically 100 µm), requiring time-consuming preparations, and have a thermodynamic limit to their sensitivity of 59 mV.Log[C]-1. Such configuration hinders the development of high-performance ion sensors due to the inherent limitations of the bulk diffusion of ions inside sensors. Consequently, they cannot be applied for high-precision applications that require high sensitivity. Furthermore, the research of anion monitoring is hampered due to the limited availability of molecular receptors with acceptable performances. We overcome such limitations by using a 300 nm nanostructured sensing film based on a novel nanoporous ion imprinted core-shell silica/gold nanoparticulate sensing film. The novel sensing film was highly selective towards chloride ions when compared to other anions such as nitrate, sulphate and carbonate. Moreover, this nanostructured sensing film exhibited above 3-fold higher sensitivity (-186.4 mV.Log[C]-1) towards chloride ions when compared to commercial devices. Such breakthrough has led to the fabrication of the smallest and most sensitive reported anion sensor working on open circuit potentiometry, with an exceptional selectivity towards chloride ions.