Our study shows the successful synthesis of gem-(Bpin,Bpin)-cyclobutanes from gem-diborylatedalkenes and olefins, demonstrating high functional group tolerance and excellent regioselectivity. Furthermore, this methodology is extended to incorporate α-methylstyrene derivatives, revealing an intriguing 1,5-hydrogen atom transfer (1,5-HAT) pathway in addition to the desired cyclobutane products. Deuterium labeling studies confirmed this unusual pathway.