A multiwall carbon nanotubes (MWNTs)-chitosan modified glassy carbon electrode (GCE) exhibits attractive ability for highly sensitive cathodic stripping voltammetric measurements of bromide (Br − ). In pH 1.8 H 2 SO 4 solution, a substantial increase in the stripping peak current of Br − (compared to bare GCE and chitosan modified GCE) is observed using MWNTs-chitosan modified electrode. Operational parameters were optimized and the electrochemical behaviors of Br − were studied by different electrochemical methods. The kinetics parameters were measured, the number of electron transfer (n) was 1 and the transfer coefficient (α) is 0.17. A wide linear calibration range (3.6×10 −7 –1.4×10 −5 gmL −1 ) was achieved, with a detection limit of 9.6×10 −8 gmL −1 . The mechanism of electrode reaction was fully discussed.