This work presents the fabrication of Nafion (Nf) or Nafion/Multiwalled Carbon Nanotubes (Nf/MWCNTs) modified gold microarray (Au-µA) and macro-(Au-M)electrode biosensors. The surface morphologies of the above electrodes were examined using SEM. The catalytic properties of the above electrodes towards dopamine were tested using square wave voltammetric technique. The Nf/MWCNT/Au-µA electrode exhibited a wide range (0.1–1000 nM) of linearity among the other electrodes. The LOD of Nf/MWCNT/Au-µA electrode was 50 pM for dopamine in the presence of 5000 µM ascorbic acid. Therefore, the Nf/MWCNT/Au-µA biosensor was applied for the determination of dopamine in human serum.