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Borylation has become a powerful method to synthesize organoboranes as versatile building blocks in organic synthesis, medicinal chemistry, and materials science. Copper-promoted borylation reactions are extremely attractive due to the low cost and non-toxicity of the copper catalyst, mild reaction conditions, good functional group tolerance, and convenience in chiral induction. In this review, we mainly updated recent advances (from 2020 to 2022) in the synthetic transformations in C=C/C≡C multiple bonds, and C=E multiple bonds mediated by copper boryl systems.