Ni-B/Cu electrode prepared by the electroless deposition technique of chemical reduction of nickel ethylenediamine complex with BH4- was characterized by SEM, XRD and XPS techniques, respectively, and evaluated using ethanol electrocatalytic oxidation by the method of cyclic voltammetry. The as-prepared Ni-B/Cu electrode exhibited much higher electrocatalytic activity than the Ni-B/Cu electrode obtained via direct reduction of nickel metallic ions. The effects of the nickel ethylenediamine complex can be attributed to both the structural effect and electronic effect. The nickel ethylenediamine complex can not only make an electroless deposition stable and highly dispersed, but also facilitate the formation of more nanoscale microcrystalline Ni on the electrode surface, which increased the electrochemical oxidation activity. Moreover, ethylenediamine influenced the electronic states of Ni and B on the electrode surface, more electrons transfer from the B to Ni that the Ni active sites became more highly unsaturated, which could promote the form of adsorbed active ethanol.