The water‐dispersible electrochormic nanocomposites, polyaniline (PANI) connected multi‐walled carbon nanotubes (MWCNTs) by covalent bond were synthesized through a grafting polymerization process of aniline monomer with functionalized MWCNTs. N,N′‐dicyclohexylcarbodiimide (DCC) was used as dehydrant for functionalization process of MWCNTs with p‐phenylenediamine (PPD). The transmission electron microscope (TEM), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FT‐IR) were used to study the morphologies, thermal stabilities and chemical structures of the nanocomposites, respectively. The UV‐vis absorbance spectra and cyclic voltammetry behaviors of nanocomposites were tested by UV‐vis spectrometer and electrochemical workstation, respectively. It is shown show that PANI‐MWCNTs nanocomposites not only exhibit good water solubility, but also exhibit excellent film‐forming properties. The results confirm that the π‐π interactions and interfacial covalent bond between PANI and MWCNTs endow PANI‐MWCNTs excellent electrochemical and electrochromic properties. The conductive network composed of PANI and MWCNTs can significantly improve the ion transports, electron conduct and electrochromic performance of PANI. The PANI‐MWCNTs‐0.6% nanocomposite film shows highest optical contrast value (0.78) and shortest response time (3.8 seconds for coloring and 3.2 seconds for bleaching) among neat PANI and PANI‐MWCNTs nanocomposites.