We prepared the polyazomethine/MWCNTs nanocomposites varying in the nanofiller loading (from 0 to 1.5 wt%). Taking into account an upshift of the characteristic D and G bands of MWCNTs in the Raman spectrum of the nanocomposite, we confirmed the interfacial interactions between MWCNTs and polymer chains. When we studied the nanocomposites morphology, we concluded that both disentanglement and dispersion of MWCNTs in the polymer matrix are provided by interfacial interactions. Using broadband dielectric spectroscopy technique, we investigated the interfacial polarization in the nanocomposites. We found that this phenomenon is valuable for electrical conductivity of the nanocomposites with high MWCNTs loading, particularly, at high temperatures and low frequencies.