As one of the keystones of electrochemistry, the oxygen reduction reaction (ORR) offers an enthralling approach to oxygen monitoring, and energy conversion/storage. At present, only 3d transition metals (TMs)-based catalysts have proven to be reliable options for electrochemical O2 activation, while non-3d TM catalysts such as 5d tungsten (W) typically exhibit much lower electrochemical ORR activities. Herein, we propose a simple and controllable approach for accelerating the ORR and oxygen evolution reaction (OER) on the surface of tungsten carbides coordinated with 3d metal, i.e., TM3W3-xC (TM=Mn, Fe, Co, Ni, and Cu). Among them, Mn3W3-xC is found to display exceptional ORR activity (Eonset = 0.83, and E1/2 = 0.73 V), which is on par with that of the commercial Pt/C catalyst (Eonset = 0.84, and E1/2 = 0.75 V) in alkaline media. Furthermore, Mn3W3-xC has outperformed Pt/C in terms of durability and methanol resistance due to the carbon shell protecting the metal nanoparticles from agglomeration or dissolution in alkaline media. The coordination of Mn centers to the W3-xC surface not only allows the precise regulation of the electronic structure of W ions but also creates dual-metal sites (MnW) to facilitate interfacial charge transfer. Such electron transfer enables the MnW surface more electrophilic, in turn increasing its affinity for hydroxide ions. As a result, the MnW coordinated with the carbide surface has OER-favorable MnW-oxo and MnW-hydroxo configurations within their oxidized surfaces. Overall, this research discovered that the catalytic potential of inactive W elements in oxygen electrochemistry can be unlocked by coordinating with 3d TMs.