Multi-walled carbon nanotubes (MWCNTs) were functionalized with a carboxyl group (-COOH) to improve their dispersion in a nylon6 (PA6) matrix, a liquid crystal polymer (LCP) and their blend. This functionalized MWCNTs also achieved better interfacial adhesions with both polymer matrices and with both phases in the blend. The dispersion of MWCNT-COOH in the polymer matrices and their interfacial interactions with polymer molecules were found to be the most important factors affecting the properties of composites. Moreover, studies on morphological, rheological, and mechanical properties confirmed that a better miscibility between PA6 and LCP had been constituted in the presence of MWCNT-COOH. Therefore, it is observed that the functionalized MWCNTs not only played the traditional role as reinforcing fillers in the polymer matrices, but also performed a novel role as compatibilizers for their blend.