In this work an optical fiber sensor, where a lossy‐mode resonance (LMR) effect was obtained due to indium tin oxide (ITO) thin overlay, has been simultaneously applied as a working electrode in a 3‐electrode cyclic voltammetry electrochemical setup. Since LMR conditions highly depend on refractive index of a surrounding medium, an LMR‐based sensor was applied for optical investigations of electrolyte's properties at the ITO surface. We have found that the optical response of the sensor highly depends on the applied potential and its changes, as well as the properties of the investigated electrolyte, i. e., its composition and presence of a redox probe. Both optical and electrochemical response of the ITO‐LMR sensor to various concentrations of phosphate‐buffered saline (PBS), NaCl and Na2SO4, as well as scan rate were investigated and discussed. We have found that the responses in optical and electrical domains differ significantly and may deliver supplementary information about the investigated analyte.