Ni foam supported-NiCo2O4 nanostructures with various morphologies are successfully prepared by a facile template-free method. The synthesis involves the electrodeposition of the bimetallic (Ni, Co) film on Ni foam support. The NiCo2O4 nanostructures are formed by immersing the bimetallic film in an oxalic acid solution, followed by a calcination progress. The control over NiCo2O4 nanostructures with different morphologies is achieved by adjusting the electrodeposition time and immersing time. The electrode is characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. H2O2 electrooxidation and electroreduction in KOH solution on the NiCo2O4 nanostructures are studied by cyclic voltammetry and chronoamperometry. Results show that NiCo2O4 nanostructures exhibit high performance and superior stability for both H2O2 electrooxidation and electroreduction, resulting from hierarchical porous structure inside their architectures. (C) 2014 Elsevier B.V. All rights reserved.