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The wetting behavior of molten Zn and Zn-Sb alloy and X80 steel in a high vacuum environment was studied by the modified sessile drop method. The wetting morphology and interface structure were analyzed by scanning electron microscope and energy dispersive spectrometer. The results show when the content of Sb in Zn-Sb alloy increases from 0.0 wt. % to 1.0 wt. %, the initial contact angle between the droplet and the substrate decreases from 102.8° to 82.5°, and the equilibrium contact angle also decreases from 57.4° to 41.4°. Sb element in the Zn-Sb alloy can reduce the contact angle and improve the wettability due to its smaller surface tension. The spreading process of Zn-Sb alloys on X80 steel can be divided into rapid adsorption, reaction control, steady-state equilibrium stages, and Zn-Sb alloys with different mass fractions have the same spreading kinetics. The volatilized Zn element in the Zn-Sb alloy will reduce the oxide film on the surface of the substrate, making it easier for the Zn-Sb droplet to wet the steel plate and induce the formation of a precursor film. The formation mechanism of the precursor film is the subcutaneous penetration mechanism.