Multi-components active metal oxide-supported catalysts are highly promising in heterogeneous catalysis due to some special promoting effects. In this study, by the controllable amount of Cu, Cu-Fe decorated anionic surfactant-templated mesoporous silica (Cu (x) Fe/AMS) was directly prepared. The obtained catalysts were characterized by X-ray diffraction, N-2 adsorption-desorption, inductively coupling plasma emission spectroscopy, scanning electron microscopy, transmission electron microscopy, UV-visible, hydrogen temperature-programmed reduction, and X-ray photoelectron spectroscopy techniques. The results revealed that bimetallic Cu-Fe oxides were directly formed and highly dispersed in the mesochannels during the calcinations and the introduction of Cu2+ and Fe2+ on the micelles has influence on the structure properties. As compared to the monometallic Fe-modified AMS, the presence of Cu promotes the effects between Fe species and silica wall, leading to the better dispersion of Fe in the mesochannels of AMS. Finally, a series of Cu-Fe-modified AMS were used as Fenton-like catalysts and exhibited good catalytic activity in the degradation of methylene blue (MB), which resulted from high dispersion of Fe species and synergetic effect between Cu and Fe active sites. 1.0 was the optimum molar ratio of Cu2+ to Fe2+ ions to achieve the best catalytic activity and stability.