AbstractElectrochemical Faradaic impedance spectroscopy was applied to evaluate dependence of the electrical resistance on human teeth. The experiments were performed using iodide anions as a redox probe to model permeability of teeth for fluoride upon an iontophoresis process. Tooth molars were used – as these are teeth most affected by tooth decay processes in vivo. Teeth compared included sound molars – with no evidence of pit and fissure decay, teeth with pits and fissures regarded ‘clinically’ as showing signs of decay, and teeth with crowns removed to present exposed dentin surfaces. A difference of more than an order of magnitude in electrical resistance was observed between sound molars and those regarded as showing evidence of tooth decay processes. Sound dentin, as expected from structural considerations demonstrated significantly lower resistance when compared to sound molars. Importantly, the difference in tooth resistance measured between carious and sound molars was shown to be much more representative of their structural integrity than comparison of digitally processed images of the teeth. The results support the utility of electrochemical Faradaic impedance spectroscopy for the development of understanding on how tooth electrical resistance may vary according to structural changes. This understanding may be useful to continued refinements in the use of electrical resistance measures as caries diagnostics and support generically the potential for iontophoretic processes in in‐office fluoride treatments of teeth.