Metal/metal hydroxide hybrid heterostructures exhibits superior performances in diverse research fields, especially in catalysis due to the presence of ample grain boundary interfaces and the strong metal/metal hydroxide synergistic actions. Herein, Co(OH)(2)-Ni hybrid heterostructures with a crystalline Ni and Co(OH)(2) is prepared on the cotton fabric substrate by a simple electrochemical process. The CCo(OH)(2)-Ni hybrid heterostructures are explored as a highly active catalyst for the electro-oxidation of hydrazine in an alkaline medium. The existence of ample grain boundary interfaces and promotional synergistic effect between the nanocrystalline metallic Ni and Co hybrid heterostructures lead to a very low-onset hydrazine oxidation potential of -0.06 V vs RHE. Moreover, the Co(OH)(2)-Ni hybrid heterostructured electrode exhibits excellent long-term catalytic stability. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.