The　application　scope　of　metal-organic　frameworks　(MOFs)　is　severely　restricted　by　their　weak　chemical　stability　and　limited　pore　size.　A　robust　MOF　with　large　mesopores　is　highly　desired,　yet　poses　a　great　synthetic　challenge.　Herein,　two　chemically　stable　Ni(II)-pyrazolate　MOFs,　BUT-32　and　-33,　were　constructed　from　a　conformation-matched　elongated　pyrazolate　ligand　through　the　isoreticular　expansion.　The　two　MOFs　share　the　same　sodalite-type　net,　but　have　different　pore　sizes　due　to　the　network　interpenetration　in　BUT-32.　Controlled　syntheses　of　the　two　MOFs　have　been　achieved　through　precisely　tuning　reaction　conditions,　where　the　microporous　BUT-32　was　demonstrated　to　be　a　thermodynamically　stable　product　while　the　mesoporous　BUT-33　is　kinetically　favored.　To　date,　BUT-32　represents　the　first　example　of　Ni-4-pyrazolate　MOF　whose　structure　was　unambiguously　determined　by　single-crystal　X-ray　diffraction.　Interestingly,　the　kinetic　product　BUT-33　integrates　2.6　nm　large　mesopores　with　accessible　Ni(II)　active　sites　and　remarkable　chemical　stability　even　in　4　M　NaOH　aqueous　solution　and　1　M　Grignard　reagent.　This　MOF　thus　demonstrated　an　excellent　catalytic　performance　in　carbon-carbon　coupling　reactions,　superior　to　other　Ni(II)-MOFs　including　BUT-32.　These　findings　highlight　the　importance　of　kinetic　control　in　the　reticular　synthesis　of　mesoporous　MOFs,　as　well　as　their　superiority　in　heterogeneous　catalysis.