Development of highly active and durable non-precious metal bi-functional electrocatalyst for both oxygen reduction and evolution reaction (ORR and OER) remains a significant challenge. Herein, porous mixed spinel MnCoxO4 was loaded on the N-doped multi-walled carbon nanotubes (MnCoxO4/NCNT) through a facile one-pot hydrothermal method to work as a bi-functional oxygen electrocatalyst. Physical characterizations confirm that the MnCoxO4 nanoparticles are composed of mixed spinel-type Co2MnO4 and (Co, Mn)[Mn, Co](2)O-4 with a diameter of 5-10 nm, which are dispersed on NCNT with secondary aggregation and resultant porous structure. Electrochemical measurements show that the MnCoxO4/NCNT catalyst exhibits high ORR catalytic activity with a dominant four-electron ORR catalytic pathway, remarkable durability, excellent methanol-tolerance, as well as superior OER catalytic activity with significantly decreased overpotential of 0.479 V in alkaline media. The multiple valence states of Co and Mn ions in MnCoxO4 coupled with the enlarged specific surface area with the help of NCNT exert crucial roles for the superior catalytic performance for both ORR and OER. Such a bi-functional oxygen electrocatalyst based on mixed spinel MnCoxO4 provides a new direction for developing low-cost, highly efficient, and robust multiple valence states transition metal-based electrocatalysts for oxygen electrode. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.