In this paper, the effect of electric field enhancement on Pt/nanostructured ZnO Schottky diode based hydrogen sensors under reverse bias condition has been investigated. Current–voltage characteristics of these diodes have been studied at temperatures from 25 to 620 °C and their free carrier density concentration was estimated by exposing the sensors to hydrogen gas. The experimental results show a significantly lower breakdown voltage in reversed bias current–voltage characteristics than the conventional Schottky diodes and also greater lateral voltage shift in reverse bias operation than the forward bias. This can be ascribed to the increased localized electric fields emanating from the sharp edges and corners of the nanostructured morphologies. At 620 °C, voltage shifts of 114 and 325 mV for 0.06% and 1% hydrogen have been recorded from dynamic response under the reverse bias condition.