Operating overvoltage occurs when the pantograph or main breaker of an electric locomotive is operated, which is prone to causing insulation failure of high-voltage equipment. The HXD1 electric locomotive is taken as the research object in this paper to explore the characteristics and influencing factors of operating overvoltage. Under pantograph lifting, main breaker closing, main breaker opening, and pantograph dropping, operating overvoltage waveform in the high-voltage system is recorded by a high-speed oscilloscope and resistance–capacitance voltage divider to analyze the overvoltage characteristics and distribution law. Tested data show that the amplitude of operating overvoltage is in the range of 80 to 330 kV with ultra-high steepness, which is similar to the Very Fast Transient Overvoltage (VFTO) in power systems. The maximum overvoltage during the entire test occurred during the main breaker closing and its amplitude is 328.60 kV with a steepness of 4.21 × 104 kV/μs. The max overvoltage of the other operations (pantograph lifting, main breaker opening, and pantograph dropping) are 280.60 kV, 194.73 kV, and 305.56 kV with ultra-high steepness. High-amplitude overvoltage is predominantly located at the pantograph, while the low-amplitude sort is mainly observed around other high-voltage equipment. The result indicates that operating overvoltage belongs to ultra-fast transient overvoltage and its amplitude and steepness are higher than existing research.