We reported a series of HKUST-like MOFs based on multiple copper-containing secondary building units (SBUs). Compound 1 is constructed by two SBUs: Cu-2(CO2)(4) paddle-wheel SBUs and Cu2I2 dimer SBUs. Compound 2 has Cu-2(CO2)(4) paddle-wheel SBUs and Cu4I4 SBUs. Furthermore, compound 3 possesses Cu-2(CO2)(4) paddle-wheel SBUs, Cu2I2 dimer SBUs, and Cu(CO2)(4) SBUs. These compounds are promising materials for CO2 capture and separation, because they all display commendable adsorption of CO2 and high selectivity for CO2 over CH4 and N-2. It is worthy to note that compound 1 exhibits the highest BrunauerEmmettTeller surface area (ca. 901 m(2) g(1)) among the MOF materials based on CuxIy SBUs. In addition, compound 3 is the first case that three copper SBUs coexist in MOFs.