The electrochemical performance of phenylbutazone (PBZ) was studied using a multi-walled carbon-nanotube-modified paste electrode (MWCNT/CPE) using a variety of voltammetric tools like cyclic voltammetry (CV), linear sweep voltammetry (LSV), and square wave voltammetry (SWV). The results showed that the MWCNT/CPE exhibited remarkable electro-catalytic action towards the electrochemical oxidation of PBZ in a phosphate buffer solution of physiological pH 7 compared to a bare carbon paste electrode. The electro-kinetic parameters like heterogeneous rate constant, transfer coefficient, scan rate, pH, and involvement of electrons in electro-oxidation of PBZ was investigated. For bare CPE, the peak current was noted to be 19.53 µA with peak potential of 0.6871 V. For MWCNT/CPE, the peak current was 30.53 µA with peak potential of 0.6792 V. The anodic peak was analyzed, and the process was diffusion controlled. For the estimation of PBZ, a SWV technique was developed with great precision and accuracy, with a detection limit of 5.2 nM and a limit of quantification of 17nM, in the concentration range 1 x 10-7 to 10 x 10-6 M. The MWCNT/CPE has been used successfully for PBZ detection in injection, blood, and urine samples, with recovery rates of 98.9% to 101.5%, 96.3% to101.7% and 98.3% to 102.8%, respectively