AbstractHerein, a simple and effective approach has been proposed to enhance the interfacial strength between multiwall carbon nanotubes (MWCNTs) and polymer matrix for improving the dispersion of MWCNTs. In more detail, a soluble polyaniline derivate containing polar group (POMA) was selectively incorporated into the binary blend of poly(amide‐imide) (PAI) and MWCNTs. The surface energy and atomic force microscope measurements suggested that POMA was located at the interface of PAI and MWCNTs. Fourier transform infrared measurement indicated that POMA simultaneously interacted with MWCNTs and PAI by hydrogen bonding and π–π interaction, providing stronger interfacial strength between conductive filler and polymer matrix. As a result, the dispersion of MWCNTs and the surface roughness of PAI composites were obviously improved, which is helpful for charge and load transfer in the PAI/MWCNTs/POMA ternary films. As a result, the conductivity increased by 250% from 13 S m−1 for PAI/MWCNTs binary composites to 48 S m−1 for PAI/MWCNTs/POMA ternary composites, and the tensile strength increased from 52 MPa for PAI/MWCNTs binary composites to 66 MPa for PAI/MWCNTs/POMA ternary composites. These findings imply that polar aromatic polymers with suitable surface energy will be a desirable compatibilizer for optimizing the dispersion of carbon nanotubes in the polymer matrix.