Carbon　dioxide　capture　and　separation　are　of　great　importance　for　cutting　greenhouse　gas　emissions.　A　series　of　Zr(IV)-based　MOF　UiO-67-MIMS(x)　(0　＜=　x　＜=　1)　derived　from　mixed　linkers　4,4＇-biphenyl-dicarboxylate　linker　(BPDC)　and　its　derivative　bearing　imidazolium　sulfonate　(BPDC-MIMS)　at　the　2-position　were　designed　and　synthesized.　Their　pore　sizes　and　structures　are　well　tuned　by　varying　the　x　ratio　of　the　two　mixed　linkers.　Binary　ionic　liquid　moieties　(MIMS/salt)　were　furnished　by　subsequently　incorporating　the　sodium　salts　within　UiO-67-MIMS(x),　engendering　a　series　of　ionic　liquid-decorated　MOF　composites,　namely,　UiO-67-ILs-anion　(anion　=Cl-,　ClO4-,　BF4-,　PF6-).　The　optimal　pore　size,　the　imidazolium　sulfonate　group　with　affinity　sites　to　CO2,　and　various　anions　of　ionic　liquid　moieties　have　a　synergistic　effect　on　the　CO2　adsorption　and　separation.　UiO-67-ILs-Cl　([Zr6O4(OH)(4)　(BPDC-MIMS)(1.5)(BPDC)((4.5))]-NaCl)　exhibited　a　high　uptake　of　CO2　of　85.20　cm(3)/g　(273　K　and　1　atm),　and　its　infinite　dilution　selectivity　of　CO2/N-2　reached　36.56.　All　composites　were　characterized　through　powder　X-ray　diffraction　(PXRD),　N-2　adsorption　isotherms,　CO2-selective　adsorption　study,　FT-IR　spectroscopy,　energy　dispersive　X-ray　(EDX)　spectroscopy,　and　thermogravimetric　analysis　(TGA).　The　CO2　adsorption　and　selective　roles　of　such　MOF-based　composites　were　systemically　investigated　by　experimental　and　theoretical　methods.