An　isoreticular　metal-organic　framework　(MOF)　series　was　constructed　from　nickel　or　cobalt　nodes,　phosphonate　monoester,　and　bipyridine　linkers.　The　cobalt-containing　MOFs　were　found　to　catalyze　the　dehydrogenative　C-H　borylation　of　alkenes　under　mild　conditions.　This　process　selectively　generates　vinyl　boronate　without　the　formation　of　alkyl　boronate　byproducts　and　is　insensitive　to　air,　enabling　large-scale　preparation　of　the　target　products　with　isolated　yields　of　over　80%.　©　2025　American　Chemical　Society.