A unique and irregular form distorted Cu2(V2O7) sphere with crumbled sheets of rGO nanocomposite was developed as a sensor over a glassy carbon electrode (GCE). It showed a higher sensitivity for an antipsychotic drug, pimozide (PMZ). Voltammetric techniques were used to investigate the electrochemical behavior of PMZ. The formation of Cu2(V2O7)-rGO nanocomposite was confirmed by X-ray diffraction analysis. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to examine the surface morphology and its properties. Cyclic voltammetric studies revealed that PMZ displayed intense electrocatalytic activity and exhibited an electro-oxidation peak at the modified electrode. The modified electrode possessed unique qualities such as fast electron transfer ability, repeatability, and reproducibility. The proposed differential pulse voltammetric (DPV) and square wave voltammetric (SWV) methods showed linearity in the concentration range of 5.12 × 10−9 M to 3.06 × 10−4 M and 1.02 × 10−9 M to 5.30 × 10−4 M, respectively. The limit of detection (LOD) was calculated to be 1.70 × 10−10 M and 8.52 × 10−11 M, while the limit of quantification (LOQ) was found to be 5.66 × 10−10 M and 2.84 × 10−10 M, respectively, for DPV and SWV methods. The developed methods were successfully applied for the determination of PMZ in pharmaceutical formulations and human urine samples.