Mesoporous silica containing multiple organometallic active sites is synthesized using a traditional post-synthesis complexation technique and a surfactant-directed assembly approach. Systematic spectroscopic studies and structure analysis indicate that catalytic mesoporous silica with controlled composition and pore structure can be readily synthesized. Catalytic performance examined by an aqueous medium two-step cascade reaction indicates that these materials possess excellent catalytic activity, reusability, and an interesting synergic effect. This work provides novel synthesis platforms towards Multifunctional catalysts for more efficient chemical transformations.