alkynes and alkenes undersolvent‐ and ligand‐freeconditions in air. The cis‐1,2‐diborylalkenes and 1,2‐diborylalkanes were obtained in moderate to excellent yields following, in most cases, a simple filtration workup protocol. The versatility of the cis‐1,2‐diboronvinyl compounds was demonstrated in a series of organic transformations, including the Suzuki–Miyauracrosscoupling and the boron–halogen