A three-dimensionally ordered macroporous (3DOM) Ni–yttria stabilized zirconia (YSZ) anode with a YSZ thin electrolyte layer was developed by a colloidal crystal templating method in order to lower the operating temperature of solid oxide fuel cells due to a high and uniform electrochemical interface that originated from a 3DOM structure. In the present study, polystyrene beads were used as the template. The anode structure was strongly influenced by the of the suspension, and it was optimized to 1.8 according to the zeta-potential measurement and scanning electron microscope observation. The 3DOM anode and thin electrolyte layer were simultaneously formed by sintering the deposit that was obtained by filtering two kinds of suspensions by turns. Here, we successfully obtained a 3DOM anode with high porosity of 72% and a thin YSZ layer on it, which was favorable in reducing both electrolyte and polarization resistances.