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The adsorption of acetylene on a Si(111) (7 × 7) surface has been studied at 300 K using high-resolution electron energy loss spectroscopy. Acetylene is predominantly adsorbed non-dissociatively, and is rehybridized having a state of hybridization between sp² and sp³. An adsorbed structure is proposed in which acetylene is di-σ bonded to two adjacent surface Si atoms saturating the dangling bonds.