The often-overlooked electrocatalytic bridge-site poisoning of the emerging dual-atom catalysts (DACs) has aroused broad concerns very recently. Herein, based on surface Pourbaix analysis, we identified a significant change in the electrochemistry-induced surface coverages of DACs upon changing the intermetal distance. We found a pronounced effect of the intermetal distance on the electrochemical potential window and the type of pre-covered adsorbate, suggesting an interesting avenue to tune the electrocatalytic function of DACs.