A double-walled MOF [Zn-5(mu(3)-OH)(2) (DBTA)(2)(H2O)(4)]center dot solvents [1, H(4)DBTA = 2,2'-dihydroxy-1,1'-binaphthyl-3,3',6,6'-tetrakis-(4-benzoic acid)] has been designed and constructed based on a rare Zn-5 cluster. The resultant sample has enrichment of porous structure with high BET and Langmuir surface area. By virtue of multiaperture structure and plentiful catalytic sites of Bronsted (-OH) and Lewis acidic (Zn-II), MOF 1 is a unique catalyst to synthesize cyclic carbonates from CO2 and epoxides with preferable repeatability.