It is now well known that at the nanoscale matters behave differently compared to bulk phases. Increased reactivity, deviations in structural, thermodynamic and kinetic properties make nanoscale materials and processes attractive for both fundamental research and applications. Here we show that nanometer thin films of materials with dielectric properties at the macroscopic level such as SiO2, Ta2O5 and HfO2 behave as solid electrolytes and exhibit evident ionic transport and electrochemical redox reactions. Experimental studies demonstrate that classical electrochemical potentiodynamic and steady state methods can be used to study the mass and charge transport at the nanoscale. We believe these reported properties of nanomatter open new opportunities for fundamental research and applications.