A facile method is to prepare novel CeMo_xO_y-clay hybrid catalysts with layered structures by using organic cation modified clay as support. During the preparation process, cerium cations and molybdate anions are easily adsorbed and impregnated into the interlamellar space of the organoclay, and after calcination they undergo transformation to highly dispersed CeMo_xO_y nanoparticles within the interlamellar space of the clay. As expected, the prepared CeMo_0.15O_x-OC-T catalysts with layered structures had high selective catalytic reduction (SCR) activity such as high NO_x conversion of >90% in the wide temperature range of 220–420 °C. Meanwhile, they also exhibit high stability and tolerance to water vapor (5 vol%) and SO₂ (200 ppm), demonstrating that these novel catalysts could serve as a good alternative for NH₃-SCR in practical application.