Multi-walled carbon nanotubes (MWCNT) have been widely used to fabricate composite electrodes due to their electrochemical properties. MWCNTs can be fabricated by various approaches and a range of MWCNT types and sizes has been developed. This study focuses on understanding the influence MWCNT diameter and specific surface area has on the electrochemical properties of a composite electrode. MWCNTs with fixed length range and diameters ranging from 10–20 to 50–80 nm were examined in this study. The amount of MWCNT utilised to fabricate the electrodes was identical and above the percolation threshold. MWCNT electrodes fabricated with larger diameters showed enhanced thermodynamic and kinetic properties towards common redox species which covered surface-insensitive, surface-sensitive and adsorption-based processes. Overall, these findings indicate that the number of strands of MWCNT alone is not essential for enhanced conductivity in composite materials but other geometric parameters play important roles.