Herein, we reduced the ZnO-modified copper phyllosilicate to synthesize a series of Cu/ZnO/SiO2 catalysts (xCuZn/SiO2) which were mixed with gamma-Al2O3 for dimethyl ether steam reforming (DME SR). The structure and the formation of copper phyllosilicate were systematically characterized by nitrogen adsorption, XRD and IR. The novel synthetic route led to the remarkably high dispersion of copper species and adjustable Cu-0/Cu+ ratio on the catalyst surface, resulting in the superior catalytic performance for DME SR. The amount of Cu-0 and Cu+ sites on the catalyst surface was dramatically affected by ZnO loading, and the turnover frequency results indicated that the 4CuZn/SiO2 catalyst (Cu/Zn = 4) with the Cu-0/Cu+ ratio of I. showed the highest catalytic performance. The XPS, H-2-TPR and TEM results revealed the existence of strong interaction between Cu species and ZnO on the reduced 4CuZn/SiO2 catalyst, which suppressed the reverse water-gas reaction and prevented the sintering of copper.