Cobalt-nitrogen-doped three-dimensionally (3D) ordered macro-/mesoporous carbons (Co-N-OMMCs) have been fabricated through a dual-templating synthesis approach in a one-pot controllable procedure by the use of silica colloidal crystal (opal) as a macroporous mold and triblock copolymer Pluronic F127 as a mesoporous template. The optimal catalyst (Co-N-OMMC-0.6) exhibits comparable catalytic activity but much higher durability and tolerance of methanol in comparison with the commercial 20 wt% Pt/C catalyst for oxygen reduction reaction (ORR) in an alkaline medium. The remarkable ORR electrocatalytic performance of the Co-N-OMMC-0.6 is ascribed to the homogeneous distribution of abundant Co-N-x active sites, as well as the large surface area and efficient mass/charge transport from the unique structure combining well-ordered bicontinuous mesopores with 3D interconnected periodic macropores. (C) 2016 Elsevier B.V. All rights reserved.