We have determined the bonding geometry of monolayer Sb films deposited at room temperature (RT), 375 and 550°C on Si(100) using transmission ion channeling. These new results reveal that the surface prepared at all three temperatures is terminated by symmetric Sb-Sb dimers, with no evidence for three-dimensional growth or clustering at the lower temperatures. This is surprising in light of recent STM images that reveal locally ordered arrays of short dimer strings for the surface annealed at 550°C, but show a bumpy and disordered appearance for the surface annealed at 375°C.