AbstractSingle‐wall carbon nanotubes (SWNTs) sub‐monolayer film has been prepared by simply electrostatically adsorbing nanotubes onto a 2‐aminoethanethiol self‐assembled monolayer (SAM) on a gold bead electrode. Tapping‐mode atomic force microscopy (TM‐AFM) is used to characterize the SWNT film, which exhibits that the orientation of SWNTs on the SAM is horizontal and the surface coverage is quite low. The SWNTs modified electrode shows nearly ideal electrochemical response to Fe(CN)$\rm{ {_{6}^{3-}}}$/Fe(CN)$\rm{ {_{6}^{4-}}}$ redox probe. The electrode with such a low SWNTs coverage, however, shows good electrocatalytic behavior to cytochrome c.