High-purity semi-insulating (HPSI) 4H-SiC has been widely used as a substrate material for AlGaN/GaN high electron-mobility transistors because of its fairly good lattice match with GaN and its high thermal conductivity. To control material quality, it is important to understand the nature of the deep traps. For this purpose, we have successfully applied thermally stimulated current (TSC) spectroscopy to investigate deep traps in two HPSI 4H-SiC samples grown by physical vapor transport (PVT) and high-temperature chemical vapor deposition (HTCVD), respectively. Fundamentals of TSC spectroscopy, typical TSC spectra obtained on the two samples, and theoretical fittings of a boron-related trap (peaked at ∼ 150 K) will be presented. Based on literature data for deep traps in conductive 4H-SiC, the impurity and point-defect nature of several commonly observed TSC traps, peaked at ∼105 K (0.22 eV), ∼150 K (0.29 eV), ∼175 K (∼0.33 eV), ∼260 K (∼0.53 eV), ∼305 K (∼0.63 eV), and ∼360 K (0.91 eV), in the HPSI 4H-SiC will be discussed.