In conclusion, we have successfully devised a solution to a longstanding challenge: achieving regioselective [2+2]-cycloadditions with alkenyl-poly-boron containing. Our work has introduced an advanced and adaptable approach for constructing polyborylated cyclobutanes through visible-light-induced cycloaddition reactions driven by energy-transfer (EnT) pathways. These reactions have enabled the in-situ generation of previously elusive polymetalated biradical species, followed by selective decarbonation-type modifications of these biradicals with olefins. This has led to the creation of unique polyborylated cyclobutane structures, which belong to a category lacking efficient synthetic methods at present times.