The monitoring of hypertension drugs is very critical and important to sustain a healthy life. In this study, we have synthesized nickel oxide (NiO) nanostructures using potassium dichromate as surface modifying agent by hydrothermal method. These NiO nanostructures were found highly active for the oxidation of ADB besylate (ADB). The unit cell structure and morphology were investigated by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) techniques. The SEM study has confirmed the nano sheet like morphology and XRD analysis has described the cubic unit arrays of NiO. After the physical characterization, NiO nanostructures were used to modify the surface of glassy carbon electrode (GCE) by drop casting method. Then cyclic voltammetry (CV) was used to characterize the electrochemical activity of NiO nanostructures in the0.1 M phosphate buffer solution of pH 10.0 and a well resolved oxidation peak was identified at 0.70 V. The linear range for the NiO nanostructures was observed from 20-90 nM with a regression coefficient of 0.99 using CV. The calculated limit of detection (LOD) was 2.125 nM and the limit of quantification (LOQ) was 4.08 nM. Further to validate the CV calibration plot, an amperometry experiment was performed on the NiO nanostructures and sensors exhibited a linear range of 10 nM to 115 nM with LOD of 1.15 nM. The proposed approach was successfully used for the determination of ADB from commercial tablets and it reveals that the sensor could be capitalized to monitor ADB concentrations from pharmaceutical products. The use of potassium dichromate as a surface modifying agent for the metal oxide nanostructures may be of great interest to manipulate their crystal and surface properties for the extended range of biomedical and energy related applications.