Elucidating the reaction mechanism of hydrazine oxidation reaction (HzOR) over carbon-based catalysts is highly propitious for the rational design of novel electrocatalysts for HzOR. In present work, isolated first-row transition metal atoms have been coordinated with N atoms on the graphite layers of carbon nanotubes via a M-N₄-C configuration (MSA/CNT, M=Fe, Co and Ni). The HzOR over the three single atom catalysts follows a predominant 4-electron reaction pathway to emit N₂ and a negligible 1-electron pathway to emit trace of NH₃, while their electrocatalytic activity for HzOR is dominated by the absorption energy of N₂H₄ on them. Furthermore, FeSA/CNT reverses the passivation effect on Fe/C and shows superior performance than CoSA/CNT and NiSA/CNT with a recorded high mass activity for HzOR due to the higher electronic charge of Fe over Co and Ni in the M-N₄-C configuration and the lowest absorption energy of N₂H₄ on FeSA/CNT among the three MSA/CNT catalysts.