To investigate these challenges, this work presents a series of programmed strategies involving three designed pathways employing gem-diborylalkenes 25,28-30 1, 1,1,2-triborylated alkenes 4, and remarkably the 1,1,2,2 tetraborylalkenes 23 6 that can operate by EnT to these polyborylated alkenes 1, 4 and 6 affording regioselectively the polyborylated cyclobutanes 3, 5, and 7 respectively (3' and 5' not formed; Figure ). One factor that could be significant is that the boryl units i.e., Bpin, can adjust the photophysical characteristics of the attached alkene such that energy transfer is more facile compared to the other alkene component, this will avoid the formation of complex products mixture. Based on calculations, it was determined that the Bpin units lower the triplet energy (47.8, 40.9, 43.7 kcal/mol for 1a, 4a, 6a respectively) relative to other alkenes (51.9 kcal/mol for 1' and 56.16 kcal/mol for 2a ) that could be used in the [2+2]-cycloaddition (for more details in these calculations see Supporting Information page S269). These predictions support that polyborylated alkenes could likely operate by EnT first (Figure ). In addition, we explore the reactivity of the gem-diboryl-biradicals e.g., I when α-methylstyrenes 2' was used as olefin coupling partner, the reaction proceeds in a complementary manner observing an interesting 1,5-hydrogen atom transfer to the cycloaddition reaction pathway forging product 8 (Figure ). Moreover, we also investigate the synthesis applications of the cyclobutane products as presented in Figure .