A fast, reliable, accurate, precise and sensitive pH sensor device is highly demanding for the monitoring of pH in biological, clinical and food industry samples. In this research work, the effect of anions on the morphology of cobalt oxide (Co3O4) nanostructures is investigated using low temperature chemical approach for the growth. Different anions have shown visible effect on the morphology of Co3O4 nanostructures. Scanning electron microscopy, X-ray diffraction and transmission electron microscopy techniques were used for the material characterization. This study has shown highly dense, uniform and good crystal quality of fabricated Co3O4 nanostructures. The nanostructures obtained from the cobalt chloride were used for the development of potentiometric pH sensor electrode. The pH sensor electrode showed excellent linearity and close to Nernstian response for the pH range of 3-13 with a sensitivity of -58.45 mV/pH. Moreover, the proposed sensor showed a fast response time of 53 s, and acceptable reducibility and repeatability. The highly sensitive and a fast time response of the proposed sensor device indicate its potential application for the monitoring of pH from real samples including biological fluids. (C) 2014 Elsevier B.V. All rights reserved.