The properties of the carbon nanotube powder microelectrodes (denoted CNTPME) are remarkably altered by anodic pretreatment and preadsorption of mediators. It seems that anodic pretreatment leads the long and tangled carbon nanotubes to be partially cut shorter, resulting in more openings as shown by TEM. Besides, the anodic pretreatment may adjust the hydrophobicity of nanotubes to match with that of Os(bpy)32+. As a result, the real surface area and the ability of adsorbing mediator Os(bpy)32+ of the nanotubes are markedly increased so as to effectively catalyze NO2- reduction in acidic solution. The properties of the carbon nanotube powder microelectrodes (CNTPME) are remarkably altered by anodic pretreatment and preadsorption of mediators. It seems that anodic pretreatment leads the long and tangled carbon nanotubes to be partially cut shorter, resulting in more openings as shown by TEM. As a result, the real surface area and the ability of the adsorbing mediator Os (bpy) 32 + of the nanotubes are markedly increased so that the anodic potential of nanotubes to match with that of Os (bpy) 32+ as to catalyze NO2-reduction in acidic solution.