Fe‐based electrocatalysts are elegant due to their better performance towards the oxygen reduction reaction. Nevertheless, they commonly contain different moieties, for example Fe‐N_x, Fe, Fe₃C and N‐doped carbon, primarily the debatable assistance of these components towards ORR electrocatalysis, specifically for intermediate peroxide reduction reactions (PRR). In this paper, to explore the role of Fe‐N_x centres for PRR, a Fe‐N‐C electrocatalyst rooted in nitrogen‐doped carbon nanotubes with mesoporous structures was synthesized from a Fe/Zn‐dicyanoimidazolate framework. The use of dicyanoimidazole coordinated with iron can introduce the Fe‐N_x active sites as well as directional N‐doped carbon nanotubes, which is good for enhancing electronic conductance of the catalyst. The attained electrocatalyst shows tremendous enactment to ORR, being comparable to the activity of Pt/C in acidic and better in alkaline electrolytes. This study also reveals that Fe‐N_x active centres are responsible for less H₂O₂ production. Though the Fe‐N_x moieties and Fe₃C/Fe particles encapsulated N‐doped carbon, both are active centres for ORR, however, Fe‐N_x sites are more active than others for peroxide reduction reaction. These perceptions suggest rational methodologies for more active and consequently further durable Fe‐N‐C catalysts.