Novel ternary-metallic ZIFs are synthesized in one-step. They are then converted into highly catalytically active, three-dimensional nanoporous, polyhedral-shaped carbon microparticles containing CoCu dual-metal nanoparticles that can efficiently electrocatalyze the methanol oxidation reaction (MOR). The Co-rich material shows among the highest mass activities reported for non-noble metal MOR electrocatalysts.