A unique mechanism of splashing from a tungsten-based anode was identified during arc discharge. Splashing occurred by breakoff of a liquid metal column, which elongates after a local concavity formed on the molten anode surface. Blue–violet luminescence, emitted by cerium ions originating from additives in the tungsten-based anode, was captured before the concavity formation. The surface temperature exceeded the boiling point of the additives at the time of splashing. The measured droplet speeds suggested that an electromagnetic force contributes the high-speed ejections. Energy dispersive spectrometry mapping also exhibited a remnant of the additives on the longitudinal cross-section of the anode after arc discharge. Based on these experimental facts, the mechanism of anode splashing in arc discharge was deduced as follows: bubble formation of additives at temperatures above their boiling point, bubble bursting at the surface, micro-plasma jet generation, liquid-column elongation and breakoff under an electromagnetic force, and consequent high-speed droplet ejection.