Expanding　the　structural　diversity　of　porphyrinic　metal-organic　frameworks　(PMOFs)　is　essential　to　develop　functional　materials　with　novel　properties　or　enhanced　performance　in　different　applications.　Herein,　we　establish　a　strategy　to　construct　rare-earth　(RE)　PMOFs　with　unprecedented　topology　via　rational　functionalization　of　porphyrinic　ligands.　By　introducing　phenyl/pyridyl　groups　to　the　meso-positions　of　the　porphyrin　core,　the　symmetries　and　connectivities　of　the　ligands　are　tuned,　and　three　RE-PMOFs　(BUT　224/-225/-226)　with　new　topologies　are　successfully　obtained.　In　addition,　BUT-225(Co),　with　both　the　Lewis　basic　and　acidic　sites,　exhibits　enhanced　CO2　uptake　and　higher　catalytic　activity　for　the　cycloaddition　of　CO2　and　epoxides　under　mild　conditions.　This　work　reveals　that　the　RE-PMOFs　with　novel　topologies　can　be　rationally　designed　and　constructed　through　ligand　functionalization,　which　provides　insights　into　the　construction　of　tailored　PMOFs　for　various　applications.