Poly-N-vinylcarbazole (PNVK) prepared by free radical polymerization method was fabricated into mixed Langmuir-Blodgett (LB) films with arachidic acid (AA). Surface pressure (pi)-area (A) isotherms showed that AA not only promoted the formation of the PNVK/AA monolayers at the air-water interface, but also had a dispersion effect on PNVK. Atomic force microscopy (AFM) studies demonstrated aggregation in the PNVK/AA monolayers. The greater the PNVK content, the more the number of the PNVK aggregates. The PNVK/AA monolayers at the air-water interface could be transferred onto hydrophobic glass or indium-tin oxide conducting glass substrates to form multilayers in which the PNVK aggregates dispersed throughout a matrix of ordered stacks of AA. Defects in the PNVK/AA LB multilayers were evaluated by cyclic voltammetry using a redox couple as probe. The higher the PNVK content was, the greater the number of defects formed in the PNVK/AA multilayers. Conductivity measurement showed that the PNVK/AA LB multilayer exhibited a high conductivity anisotropy of 10(6) and the thermal conduction obeyed the Arrhenius' law.