HP-Cu-BTCs (CTAB), HP-Cu-BTC(N,N), HP-Cu-BTC(SDBS) series with open metal coordination site Cu(I), cage window sites, tunable porosity, high specific surface area, cavity, etc., were synthesized using cationic surfactant (cetyltrimethylammonium bromide, neutral organic amine, and an anionic surfactant as templates, respectively, A variety of techniques were used to analyze the materials before and after CO2 cycle adsorption at 303K. A high BET specific surface area (1,194.06m2/g) and total pore volume (0.63 cm3/g) were found in the synthesized HP-Cu-BTC(N,N). The synthesized HP-Cu-BTC(N,N) not only has high CO2 adsorption capacity (7.4293mmol/g) but also good selectivity (37.20) for adsorption separation of CO2/N2. Besides, FT-IR spectroscopy, CO2-TPD curves and adsorption kinetic curve demonstrated that the adsorption mechanism of synthesized HP-Cu-BTC(N,N) was mainly attributable to physisorption and it could be regenerated at relatively low temperature. The mesoporous structure not only improves the uptake capacity but also improves the diffusion and mass transfer of CO2. At the same time, the CO2-TPD showed that the HP-Cu-BTCs may have two major adsorption sites. One is to absorb CO2 molecules through van der Waals forces. The other is the electrostatic interaction of the open Cu sites with CO2. Therefore, the CO2/N2 adsorption selectivity of HP-Cu-BTC(N,N) is significantly higher than that of conventional Cu-BTC. After five consecutive adsorption/desorption cycles, the adsorbents retained an excellent adsorption property. Thus, it is a very good adsorbent for the CO2 capture.