[en] Graphical abstract: The homogeneously grafted PEDOT/MWCNTs containing numerous whorl fingerprint-like open ends endows with excellent electrochemical performances. Highlights: ► A ternary phase system with the surfactant AOT is utilized to efficiently solve the problem of the aggregation of MWCNTs. ► The homogenously grafted PEDOT/MWCNTs composite is synthesized by in situ chemical polymerization in the ternary phase system. ► The core–shell nanotubes contain many whorl fingerprint-like open ends that are greatly favorable for the transportation of the electrons and ions. ► The energy density of grafted PEDOT/MWCNTs has been enhanced by a factor of four comparing to that of native MWCNTs. ► The grafted PEDOT/MWCNTs composite manifests better cycle durability than both the constituents. - Abstract: The homogenously grafted composite of poly (3,4-ethylenedioxythiophene)/multiwalled carbon nanotubes (PEDOT/MWCNTs) is synthesized by in situ chemical polymerization in a ternary phase system. When carbon nanotubes are dispersed in this system containing sodium bis(2-ethylhexyl) sulfosuccinate (AOT), the surfactant AOT can efficiently hinter the aggregation of MWCNTs by absorbing and arranging regularly on the MWCNT surface. It is greatly advantageous to the stabilization of MWCNTs, which leads to the equally grafted composite. Its morphology was observed by scanning and transmission electron microscopes. Especially, the core–shell nanotubes contain many whorl fingerprint-like open ends that are efficiently favorable for the transportation of the electrons and ions. Such grafted PEDOT/MWCNTs composite nanotubes manifest enhanced electrochemical performances. We investigate the application of PEDOT/MWCNTs as a high-property supercapacitor and test its capacitive performance by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The energy density of grafted composite, 11.3 Wh kg⁻¹, has been enhanced by a factor of four comparing to that of native MWCNTs. Besides, the composite also presents better cycle durability after 1000 cycles. This composite will be a good candidate for the applications on supercapacitors.