The　design　and　synthesis　of　metal-organic　frameworks　(MOFs)　enclosed　with　multiple　catalytic　active　sites　is　favorable　for　cooperative　catalysis,　but　is　is　still　challenging.　Herein,　we　developed　a　sequential　postsynthetic　ionization　and　metalation　strategy　to　prepare　bifunctional　multivariate　Zr-MOFs　incorporating　zinc　porphyrin　and　imidazolium　functionalities.　Using　this　facile　strategy,　tetratopic　[5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]zinc(II)　(ZnTCPP)　ligands　were　successfully　installed　into　the　cationic　Zr-MOF　to　obtain　ZnTCPP(Br-)Etim-UiO-66.　These　MTV-MOFs,　including　TCPPIm-UiO-66,　TCPP(Br-)Etim-UiO-66,　and　ZnTCPP(Br-)Etim-UiO-66,　were　well　characterized　and　used　in　CO2　capture　and　conversion　into　cyclic　carbonate　from　allyl　glycidyl　ether　and　CO2　under　cocatalyst-free　and　1　bar　CO2　pressure　conditions.　It　was　found　that　the　structural　features　and　CO2　affinity　properties　of　these　MTV-MOFs　can　be　tuned　by　introducing　imidazolium　groups　or　doping　zinc　sites.　Additionally,　ZnTCPP(Br-)Etim-UiO-66　exhibited　enhanced　catalytic　activities　compared　to　other　MTV-MOFs　herein　for　obtaining　the　3-allyloxy-1,2-proplyene　carbonate　product,　which　was　attributed　to　the　cooperative　effect　of　Zn2+　sites　and　Br-　ions　in　this　microporous　ionic　MTV-MOF.　ZnTCPP(Br-)Etim-UiO-66　can　be　recycled　easily　and　used　at　least　three　times.　©　2018　American　Chemical　Society.