The sidewall structure of multi-walled carbon nanotubes (MWNTs) was successfully functionalized with poly(3-hexylthiophene) (P3HT) by a non-covalent bond method. P3HT plays an important role in dispersing MWNTs, and assists them to have a stable existence at the air/water interface. The behavior of mixed MWNT/P3HT monolayer at the air/water interface was investigated after obtaining a homogeneously dispersed solution. The effect of MWNT concentration on the mixed MWNT/P3HT monolayer was investigated using the pressure-area (pi-A) isotherm, relaxation curve and transmission electron microscopy (TEM). The mixed MWNT/P3HT monolayer was transferred onto a solid substrate using the Langmuir-Blodgett (LB) technique with horizontal or vertical deposition. The multilayer film was delicately fabricated by repeated deposition of the ultra-thin film. Scanning electron microscopy (SEM) images revealed non-uniformity in morphology of the ultra-thin MWNT/P3HT films. The absorption intensity at 250 nm by UV/vis spectroscopy illustrates that a uniform formation of mixed MWNT/P3HT monolayer into multilayer film was successfully obtained by horizontal deposition. The current-voltage characteristic of the ultra-thin MWNT/P3HT film shows that the current increases linearly with the increasing voltage, which indicates that MWNT/P3HT film forms an ohmic contact with gold. And, the electric current was estimated to be mainly contributed by MWNTs. (C) 2010 Elsevier B.V. All rights reserved.