New cobalt‐iron chalcogenide clusters C5HMe4Co(CO)E2Fe2(CO)6 (E = Se, Te) were prepared and characterized by IR and NMR spectroscopy; their structures were determined by single‐crystal XRD. Catalysts consisting of nanoparticles of bimetallic chalcogenides of cobalt and iron deposited on highly dispersed carbon black Vulcan XC‐72 were made from the synthesized clusters. Structural characteristics of these catalysts were assessed using X‐ray phase analysis (XRD), microprobe analysis (EDX), and transmission electron microscopy (TEM). It was shown that on the obtained catalysts oxygen electroreduction reaction in alkaline medium proceeds according to a four‐electron mechanism, and the catalysts are tolerant to methanol presence.