Multi-walled carbon nanotube (MWCNT)/polyaniline (PANI)/MnO2 (MPM) ternary coaxial structures are fabricated as supercapacitor electrodes via a simple wet chemical method. The electrostatic interaction between negative poly(4-styrenesulfonic acid) (PSS) molecules and positive Mn2+ ions causes the generation of MnO2 nanostructures on MWCNT surfaces while the introduction of PANI layers with appropriate thickness on MWCNT surfaces facilitates the formation of MWCNT/PANI/MnO2 ternary coaxial structures. The thickness of PANI coatings is controlled by tuning the aniline/MWCNT ratio. The effect of PANI thickness on the subsequent MnO2 nanoflakes attachment onto MWCNTs, and the MPM structures is investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and field-emission scanning electron microscopy (FESEM). The results suggest that appropriate thickness of PANI layers is important for building MPM ternary coaxial structures without the agglomeration of MnO2 nanoflakes. The MPM ternary coaxial structures provide large interaction area between the MnO2 nanoflakes and electrolyte, and improve the electrochemical utilization of the hydrous MnO2, and decrease the contact resistance between MnO2 and PANI layer coated MWCNTs, leading to intriguing electrochemical properties for the applications in supercapacitors such as a specific capacitance of 330Fg−1 and good cycle stability.