A measurement technique and analysis are presented for the accurate determination of the capture cross sections of the interface states in metal‐oxide‐semiconductor (MOS) structures. The technique utilizes the interface‐trap‐filling kinetics during measurements by energy‐resolved deep level transient spectroscopy (DLTS). High accuracy is attained by accounting in the analysis for the charge‐potential feedback effect which is a unique feature of the MOS structure and which presents a critical difficulty in the DLTS measurement of capture cross sections in MOS devices. The accurate measurement of the capture cross sections obtained in this work allows us to study several electronic properties of the Si‐SiO2interface including (i) the behavior of the capture cross sections of interface states created by high‐field stress on MOS devices, and (ii) the determination of the capture cross section of dangling bonds at the ⟨100⟩‐oriented Si‐SiO2interface. Finally, the possibility of determining the degeneracy factor of the interface states is questioned.