Silicon carbide (SiC) has become one of the most promising materials in the field of power semiconductors in the last 20 years. Among the SiC polytypes, 4H‐SiC is considered the suitable polytype for power electronic applications due to its large bandgap, high thermal conductivity, and high electron‐saturated drift velocity. Currently, the electrically active defects in the 4H‐SiC epitaxial layer and at the interface of 4H‐SiC/SiO 2 are still the primary impediments to SiC‐based power electronics from reaching their true potential limit. These defects are responsible for the degradation of device performance over time. Therefore, analysis of these defects is critical for the control and development of SiC devices. In this review, the point defects in the 4H‐SiC epitaxial layer and 4H‐SiC/SiO 2 interface states are emphasized, and the important electrical characterization techniques for these electrically active defects are compared. The key summary of electrical characterization techniques helps to better understand electrically active defects in SiC materials, providing a precise basis for further research and material applications.