Abstract: Montmorillonite-cellulosenanofibers (MTM-CNFs) substrate materials were prepared by freeze drying. Then polyaniline (PANi) was synthesized from aniline monomers by in-situ polymerization and the ordered nanowire arrays were constructed without templates. Through the research on microstructure, synthesis mechanism, electrical conductivity and electrochemical properties of PANi/(MTM-CNFs) composite electrodes, we studied the principle of compounds prepared by one-dimensional (1D) linear material, two-dimensional (2D) nanosheets and conductive polymer. Furthermore, we also studied the preparation method of the energy-storing materials with ordered arrays. The results show that the incorporation of MTM nanosheets facilitate the in-situ growing of PANi nanorod on the substrates, Forming the ordered nanowire arrays and improving the capacitance of the composite electrodes efficiently. When the mass ratio of MTM and CNFs in the substrates is 1∶9, the PANi/(MTM-CNFs) compo-sites have the highest capacitance with the value of 596 F/g, which is 11.5 times compared to PANi/CNFs composites. With the increasement and stack of nanosheets, the capacitance of composites decreases owing to the reduced active substance. However, the value of capacitance of ternary electrodes is also significantly higher than that of binary electrodes.Furthermore, the corporation of MTM nanosheet is beneficial for the stability of columbic efficiency of the composites. During the charge and discharge cycles for 1 000 times, the value of columbic efficiency is always around 100%.