A recently proposed molecular orbital localization procedure, based on the electron localization function (ELF) technique, has been used to describe chemical bonding in the cluster series Sin(BH)5-n2- (n = 0-5). The method combines the chemically intuitive information obtained from the traditional ELF analysis with the flexibility and generality of canonical molecular orbital theory. This procedure attempts to localize the molecular orbitals in regions that have the highest probability for finding a pair of electrons, providing a chemical bonding description according to the classical Lewis theory. The results confirm that conservation of the structures upon isoelectronic replacement of a B-H group by a Si atom, allowing evolution from B5H52- to Si52-, is in total agreement with the preservation of the chemical bonding pattern. © 2013 American Chemical Society.