In the present paper, Na3BiO4–Bi2O3 films have been tested for hydrogen ion sensing. Na3BiO4–Bi2O3 mixed oxide nanostructures were deposited on the Indium–Tin-Oxide (ITO) coated glass substrate using a low-cost electrodeposition technique at room temperature. The nanostructures have been characterized using FESEM and XPS to study their morphology and composition, respectively. Vertically aligned nanostructures (thickness~90 nm) with well-defined edges were seen in FESEM studies. XPS analysis indicates the presence of Na3BiO4 and Bi2O3. The crystallinity and the mixed phase of the film were further confirmed by X-ray diffraction study. These nanostructures were explored as a potential candidate for pH sensing using them as a sensing film for Extended-Gate Field-Effect Transistor (EGFET). A sensitivity of 49.63 mV/pH has been observed with good linearity. To the best of our knowledge, for the first time vertically aligned Na3BiO4–Bi2O3 mixed oxide nanostructures are demonstrated as an EGFET-based (Hydrogen ion) pH sensor.