Chiral Si-, P-, and S-containing organic compounds with central, planar, and axial chiralities have found a plethora of applications in various fields of chemistry. Despite significant efforts to explore new catalytic methodologies and synthetic applications to access such compounds, there are still only a few examples which are low in number and limited in diversity. The catalytic construction of Si-, P-, and S-stereogenic organoheteroatom compounds is undoubtedly one of the most exciting and challenging aspects in asymmetric catalysis and the application of catalytic asymmetric C–H activation reaction for the construction of chiral organoheteroatom compounds is still in its infancy. In this Review, we highlighted the main progress on the corresponding catalytic asymmetric reactions that apply to the construction of Si-, P-, and S-stereogenic centers and related chiral organoheteroatom compounds in a catalytic C–H activation fashion.