This paper puts forward the electrical safety assessment for important power users (IPUs) based on user’s responsibility, in order to strengthen their electrical safety level. Analyses are made on the risk factors existing in operation and management. According to their progressions, the risk factors are divided into 4 categories, i.e. base-configuration risk, organization-institution risk, operation-execution risk and accident-controlling risk. Moreover, this paper establishes the index system for safety assessment based on the matter-element theory. Finally, an example is given to prove the feasibility and effectiveness of the assessment index system, which provides a new method to quantitatively assess the electrical safety for IPUs.