Si 1− x Ge x /Si heterostructures play a primary role in the Si-based fast electronics developments of today. In this work, we will present the experimental results of infrared spectroscopic ellipsometry (IRSE) for structural determination of the boron heavily doped SiGe/Si sample grown by ultra-high vacuum chemical vapor deposition (UHVCVD) (the Ge atomic percent, the thickness of SiGe film and boron concentration). Especially, the principle of boron concentration in p-type SiGe film layer determined by IRSE was elucidated in detail. In addition, in order to corroborate the validity of IRSE for determining dopant concentration, secondary ion mass spectroscopy (SIMS) experiment has also been carried out. The close experimental agreement between IRSE and SIMS demonstrate that IRSE as a contactless, and non-destructive technology can be used in-line tools in production used for measuring the Ge content, the thickness of SiGe layer and boron concentration in p-type dopant SiGe/Si heterostructure, which often used the base layer of SiGe hetero-junction bipolar transistor (HBT) devices.