New gold catalytic system prepared on ceria-modified meso-/macroporous binary metal oxide support (CeO/TiO-ZrO) and used as water-gas shift reaction (WGSR) catalyst is reported. The support was prepared through the surfactant templating technique combining with the use of mixed alkoxide solutions. Ceria-modifying additive and gold were deposited consecutively on the meso-/macroporous TiO-ZrO by deposition-precipitation method. The samples were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, N adsorption analysis, and temperature-programmed reduction. The catalytic activity of the new gold-based catalysts was evaluated in WGSR and it was compared with that of gold catalysts supported on simple and binary mesoporous oxides (TiO, ZrO, and TiO-ZrO) and ceria-modified mesoporous titania support (CeO/mTiO ). A high degree of synergistic interaction between ceria and support and a positive modification of structural and catalytic properties have been achieved. The new gold catalytic system is found to be a promising catalyst for practical WGSR application.