In this work, a novel supercapacitor electrode material named MnO2/b-PEDOT/MWCNTs is synthesized by first preparing the PEDOT hollow spheres (b-PEDOT), and then anchoring the b-PEDOT on the surface of MWCNTs. At last, wrapping MnO2 nano-grains onto the surface of b-PEDOT and these composite spherical grains form a network structure with multiwalled carbon nanotubes (MWCNTs) after the coprecipitation process. Utilizing this hybrid material, a specific capacitance of 270 F g−1 at a current density of 0.3 A g−1 is achieved. A new flexible, low cost and easy fabricated micro-supercapacitor device by using MnO2/b-PEDOT/MWCNTs nanocomposite as electrode material is assemblied, which has a relatively rectangle in shape of standard cyclic voltammetry curves, indicating excellent supercapacitor behavior and a specific capacitance of 110 F g−1 at a current density of 2 A g−1 is achieved. The CV curves of the assemblied micro-supercapacitor under different bending states showed that there is no noticeable difference of electrochemical properties after being folded.