This paper presents the electrochemical stabilization of methyl viologen cations on a variety of carbon materials using a glassy carbon electrode. Three different types of voltammetry (potential hold, triangular wave, and square wave voltammetry) were used to stabilize the methyl viologen cation. Methyl viologen cation-modified multi-walled carbon nanotubes (MWCNTs) of different diameters and with various functional groups were examined to observe the effects of carbon particle size and surface modification. Various carbon materials containing MWCNTs, acetylene black, Super P, Vulcan XC-72, and Ketjenblack were modified by methyl viologen and then electrochemically characterized. Their electrochemical behaviors are discussed in terms of carbon properties, such as pore structure and electrical conductivity. Carbon with immobilized the methyl viologen cation and glucose oxidase was assessed to confirm its feasibility for enzyme electrode applications.