Abstract: Electrochemical behavior of the antibiotic, rifampicin was studied by cyclic voltammetry using multi-wall carbon nanotubes modified GCE (MWCNT′s/GCE) as working electrode, SCE as reference electrode and Pt-electrode as counter electrode. It was shown that in a supporting electrolyte of 0.2 mol·L-1 H2SO4-Na2SO4 solution of pH 1.2, significant catalytic action on rifampicin by the modified electrode, MWCNT′s/GCE, was observed, leading to remarkable enhancement of the redox peak currents. Linear relationships between values of reduction peak current and concentration of rifampicin were obtained in the ranges of 6.6×10-8-6.8×10-6mol·L-1 and 6.8×10-6-4.8×10-5mol·L-1 separately. Value of detection limit (3S/N) found was 3.0×10-8mol·L-1. The electro-chemokinetics of the electrode reaction of rifampicin at the MWNCT′s/GCE was also studied.