Ultrahigh‐vacuum chemical vapor deposition has been exploited to grow single‐heterojunctionn‐type modulation‐doped Si/SiGe structures. Phosphorus dopant is imbedded in the SiGe layer at two distinct positions: one at the surface to prevent depletion by surface states, and the other separated from the Si heterointerface by an intrinsic SiGe spacer, to supply electrons to the two‐dimensional electron gas. With a 4‐nm‐thick spacer layer, peak mobilities of 1800 cm2/V s, 9000 cm2/V s, and 19 000 cm2/V s were measured at room temperature, 77 and 1.4 K, respectively. These are the highest values reported for this material system.