Ion-selective electrodes are at the forefront of research nowadays, with applications in healthcare, agriculture and water quality analysis among others. Despite multiple attempts of miniaturization of these polyvinyl chloride (PVC) gel-based ion sensors, no ion-sensing devices with a thickness below the micrometer range, and operating using open circuit potential, have been developed so far. This work reports the causes of this thickness limitation in potassium-selective sensors. Highly homogeneous ion-sensing films were fabricated by a method based on aerosol assisted chemical vapour deposition, leading to smooth surfaces with 27 ± 11 nm of roughness. Such homogeneity allowed the systematic study of the performance and ionic diffusion properties of the sensing films at sub-micrometer scales. Sensitivities below the Nernst response were found at low thicknesses. The nature of this reduction in sensitivity was studied, and a difference in the superficial and bulk compositions of the films was measured. An optimal configuration was found at 15 µm, with a good selectivity against Na(+) (K(K)(+)(, Na)(+) = -1.8) a limit of detection in the range of 10(-4) M and esponse time below 40 s. The stability of sensors was improved by the deposition of protective layers, which expanded the lifespan of the ion sensors up to 5 weeks while preserving the Nernst sensitivity.