The most stable form of a B₃₆ cluster has a central hexagonal hole. Such an interesting finding has led to the possible synthesis of a 2D boron sheet by employing the B₃₆ cluster as the building unit. Herein, a DFT study to investigate the reason for the central location of the hexagonal hole in the B₃₆ cluster is presented. The results show that the B₃₆ cluster with a central hexagonal hole is highly thermodynamically and kinetically stable. More importantly, such high stability is further understood through chemical bonding analysis.