In this paper, we describe the preparation of a porous nanosheet-stacked NiCo2O4 composite electrode using a novel electrophoretic deposition (EPD) calcination method. The effects of the deposition time and voltage, and of the calcination temperature have been investigated. The microstructure of the deposited films in the electrodes before and after calcination has also been investigated. The electrocatalytic properties of the electrodes have been investigated using cyclic voltammetry and polarization curves. The electrode films produced using this new technique have a porous structure composed of stacked hexagonal NiCo2O4 nanosheets. The resulting electrodes exhibit good electrocatalytic properties for water electrolysis.