In this work, a new strategy is presented to form ordered multiwalled carbon nanotube (MWNT) arrays. The MWNTs are aligned horizontally and parallel in (3-aminopropyl)triethoxysilane (3-APTES) sol films on the surface of mica and glassy carbon (GC). 3-APTES is ready to form charged rodlike micelles, which play a key role in fabricating orderly MWNT arrays. Moreover, we prepare MWNT arrays on the surfaces of solid electrodes and detect the electrochemical response of the microarray electrodes for the Fe(CN)(6)(3-)/ Fe(CN)(6)(4-) couple.