A boron‐accumulated Si(100) surface with boron coverage up to 0.1 monolayer has been prepared by high‐temperature annealing of B‐doped Si samples. Scanning tunneling microscopy has been used to monitor the transformation in surface morphology and surface atomic structure induced by boron surface accumulation. The specific boron‐induced surface features have been elucidated and a model of their atomic structure has been proposed. On the boron‐accumulated surface epitaxial Si films with a thickness of 0.1–3.0 monolayers have been grown using solid phase epitaxy and molecular beam epitaxy. The results show that under appropriate growth conditions B surface segregation can be suppressed even on the atomic scale. The effect of boron induced features on the growth process has been discussed.