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%.