Rational design and synthesis of multifunctional electrocatalysts with high-efficient activity and robust stability toward the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable, but remain a challenging step. Herein, a novel hollow bimetallic carbide/nitrogen-doped carbon nanotube (Co6Mo6C2@NCNT) is successfully synthesized through the simple pyrolysis of polypyrrole (PPy)-supported metal-organic framework (MOF) composite. Remarkable characteristics of the large surface area, hollow and porous structure, rich active sites and synergistic effect between Co6Mo6C2 and NCNT arouse high catalytic efficiency. Notably, the Co6Mo6C2@NCNT presents excellent ORR catalytic activity (a high half-wave potential of 0.875 V vs. reversible hydrogen electrode (RHE) and diffusion-limited current density of 6.22 mA cm(-2)) via a fourelectron pathway, together with outstanding stability and methanol tolerance over commercial Pt/C in 0.1 M KOH solution. The composite also exhibits superior HER performance, delivering a low over-potential of 122.14 mV at current density of 10 mA cm(-2), as well as good catalytic performance for OER in 1.0 M KOH solution. This work may provide some insight in design multifunctional electrocatalysts derived from MOF with advanced performance for sustainable energy technologies. (C) 2020 Elsevier Inc. All rights reserved.