Bifunctional electrocatalysts based on non-precious metals were developed for the dioxygen reduction and methanol oxidation reactions. These electrocatalysts can be considered as candidate cathode and anode materials for anion-exchange membrane (AEM) alkaline alcohol fuel cells. A series of Ni-doped cobalt oxide (NixCo3-xO4) hierarchical nanostructures composed of one-dimensional nanorods was prepared by an inexpensive hydrothermal method. X-ray diffraction patterns showed that the NixCo3-xO4 crystallized in a cubic spinel phase. The electrochemical performance of the catalysts was investigated using a conventional cyclic voltammetry technique. The electrocatalytic behaviour of the NixCo3-xO4 hierarchical nanostructures was compared with the behaviour of Co3O4 and Co0.33Ni0.67O. The synergistic behaviour of the Ni in the NixCo3-xO4 nanostructures was established with respect to the Ni content. NixCo3-xO4 hierarchical nanostructures show a better catalytic behaviour than Co3O4 and Co0.33Ni0.67O. Although the NixCo3-xO4 compositions all showed good catalytic behaviour, Ni1Co2O4 was identified as a superior bifunctional electrocatalyst for the oxygen reduction and methanol oxidation reactions in alkaline media. The effect of the Ni content on the electrocatalytic properties of the NixCo3-xO4 hierarchical nanostructures was clearly shown. The use of these electrocatalysts based on non-precious metals could have a commercial impact on the development of non-platinum electrocatalysts for application in AEM alkaline alcohol fuel cells.