The construction of structurally complexed and high-value chemical molecules from simple and readily available feedstocks is a long-standing challenge to chemists. Here, we describe a copper-catalyzed borofunctionalization of styrenes with B₂pin₂ and carbon monoxide. A set of new sodium cyclic borates were obtained with NaO^tBu as the base. These unique sodium cyclic borates can be easily converted into a variety of multifunctional β-boryl vinyl esters, boryl carbonates, β-boryl aldehydes, and boryl vinyl ether. In addition, the procedure also features good functional group tolerance and utilizes CO as the C1 source.