Metal-organic polyhedra (MOPs) have attracted great attention due to their intriguing structure. However, the applications of MOPs are severely hindered by two shortcomings, namely low dispersity and poor stability. Here we report the introduction of four MOPs (constructed from dicopper and carboxylates) to cavity-structured mesoporous silica SBA-16 via a double-solvent strategy to overcome both shortcomings simultaneously. By judicious design, the dimension of MOPs is just between the size of cavities and entrances of SBA-16, MOP molecules are thus confined in the cavities. This leads to the formation of isolated MOPs with unusual dispersion, making the active sites highly accessible. Hence, the adsorption capacity on carbon dioxide and propene as well as catalytic performance on ring opening are much superior to bulk MOPs. More importantly, the structure and catalytic activity of MOPs in confined cavities are well preserved after exposure to humid atmosphere, whereas those of bulk MOPs are degraded seriously.