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• Tubular Cu 2 MoS 4 /MWCNTs were prepared as supercapacitor negative electrode material. • Appropriate MWCNTs addition significantly optimized the electrochemical performance. • CMS/MWCNTs-0.15@CC exhibits a highest specific capacitance of 219F g−1 at 0.5 A g−1. • The device with a voltage window of 1.8 V yields an energy density of 24.5 Wh kg−1 at 900 W kg−1. The ternary layered Cu 2 MoS 4 (CMS) has been proven to be a potential supercapacitor negative electrode material. However, its inherent low conductivity and limited diffusion dynamics usually result in unsatisfactory specific capacitance and rate performance. Therefore, hollow tubular CMS and CMS/MWCNTs-0.05, 0.15, 0.25 composite materials were prepared by a one-pot hydrothermal method in this work. The addition of MWCNTs improves the electrical conductivity and provides an efficient three-dimensional electronic transport network. Due to the smallest resistance and optimized porous structure with large surface area, CMS/MWCNTs-0.15@CC exhibits a highest specific capacitance (C s) of 219F g−1 at 0.5 A g−1, which is 2.45 times that of CMS@CC. The assembled Ni-Co-S@CC//CMS/MWCNTs-0.15@CC supercapacitor with a voltage window of 1.8 V yields a maximum energy density of 24.5 Wh kg−1 at 900 W kg−1. [ABSTRACT FROM AUTHOR]