Developing an efficient low-cost and high performance electrocatalyst for electro-oxidation of hydrazine is one of the key challenges in the prospect of direct hydrazine fuel cell (DHFC) application. In this work, a series of nitrogen doped three-dimensional porous Co3O4/carbon nanosheet network catalysts are synthesized (Co-NPC NNs-x), and simultaneously characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and electrochemical methods. Among them, Co-NPC NNs-2 is found to be a potential electrocatalyst towards highly efficient electro-oxidation of hydrazine. The electrochemical results clearly display that Co-NPC NNs-2 catalyst shows enhanced electro-oxidation (low-onset oxidation potential, higher catalytic current response), and higher cycling stability (catalytic response retained even after 120 successive cycles) toward hydrazine when compared to Co-NPC NNs-1, Co-NPC NNs-3, and NPC NNs catalysts modified electrodes. The existence of large active surface area, higher active catalytic sites, and synergetic activity between NPC NNs and Co3O4 NPs (Co-NPC NNs-2) are vital factors mainly attributes to the superior electro-oxidation response of hydrazine. Further, the Co-NPC NNs-2 catalyst demonstrated longer durability towards the electro-oxidation of hydrazine, which is highly comparable with commercially available Pt/C catalyst. Such an efficient low-cost electrocatalyst nanomaterial can enable the use of hydrazine as a promising energy carrier for DHFCs, which increases its practicality for upcoming energy storage and conversion applications.