The objective of this paper is to determine the transient characteristics and sites of the pre-breakdown (pre-BD) in the spark conditioning under power frequency voltage (PFV) in vacuum. A multi-angle optical path system was built to record the arc of pre-BD at two viewing angles by one camera, realizing the determination of the pre-BD sites in spark conditioning. The recording rate of high-speed camera was 580,000 frames/s. The experimental results indicate that, in the spark conditioning under PFV, the pre-BDs continuously occurred at a random moment. Within several half-waves, the number of the pre-BDs could reach dozens of times, which was the key for the treatment of the electrode surface in conditioning. Under the application of PFV, the single pre-BD occurred at a random moment, in which would last for several microseconds and the peak value of the current would reach several amperes. Moreover, the pre-BD sites randomly distributed in the surface of the electrode and almost covered the whole surface of the electrode. The number of the pre-BDs in edge region of the electrode tent to be more. The pre-BDs took place independently in both time and space.