A modified electrode was fabricated by electrochemical formation of poly(vinylferrocene) on the multiwall carbon nanotube-alizarin red S matrix covered glassy carbon electrode. A higher electrochemical activity was obtained to the electrocatalytic oxidation of dopamine. The electrode surface was characterized electrochemically and spectroscopically. Poly(vinylferrocene) (PVF) in electrode was used as an electron transfer mediator in the electrochemical oxidation of compounds due to its perfect reversible redox properties. Multi-wall carbon nanotubes (MWCNTs) / alizarin red S (ARS)-PVF electrode was used to the determination of dopamine in the presence of ascorbic acid in 0.1 M sulphate buffer solution at pH 7. The performance of the MWCNTs/ARS-PVF electrode was evaluated by DPV and amperometry.