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The Bi/Si(111) (root 3 x root 3)R30 degrees trimer phase offers a prime example of a giant spin-orbit splitting of the electronic states at the interface with a semiconducting substrate. We have performed a detailed angle-resolved photoemission spectroscopy (ARPES) study to clarify the complex topology of the hybrid interface bands. The analysis of the ARPES data, guided by a model tight-binding calculation, reveals a previously unexplored mechanism at the origin of the giant spin-orbit splitting, which relies primarily on the underlying band structure. We anticipate that other similar interfaces characterized by trimer structures could also exhibit a large effect.