<p>The liquid lead–bismuth eutectic (LBE) exerts a potent corrosive effect on the austenitic stainless steel cladding material. Here, this work select five surface structures, the pristine ‘Clean’ surface, ‘Fe_vacancy’, ‘O_subs’, ‘O_subs + O_fcc’, ‘O_subs + O_hcp’, to evaluate the adsorption behavior of liquid metal atoms by energetics method. Likewise, the electronic structure of the surfaces has been analyzed to reveal the effect of vacancy defects and oxygen atoms on the dissolution corrosion behavior of this surfaces. Building upon these insights, alloying elements (Cr, Si, and Al) are considered to prevent the adsorption of Pb/Bi. Finally, this work reveals that the presence of vacancy defects enhances the adsorption ability of Pb/Bi on the surface, while the oxygen-rich environment weakens the positive effect of vacancy defects on the adsorption of Pb/Bi. These discoveries lay down a robust theoretical foundation for improving the corrosion resistance of stainless steels.</p>