<p>With the increasing impacts of global climate change, SOEC-based CO₂ capture and conversion technologies have been widely explored for sustainable energy applications. The technology of in situ exsolution of perovskite has been adopted to obtain uniform nanoparticles for enhancing the catalytic performance and tolerance of SOEC. However, the exsolution and weak catalytic activity of perovskite materials still remain unresolved challenges. Density functional theory (DFT) calculations have been conducted to identify the fundamental parameters governing nanoparticle exsolution and gas adsorption in SrTiO₃ perovskites, establishing design principles for enhanced Cu exsolution and improved catalytic performance in CO₂ and H₂O electrolysis within SOECs, through the combination of the exsolution and adsorption models to ultimately obtain the optimal selection scheme for Cu Ni-Cr surface-doped SrTiO₃. The promoted exsolution of Cu nanoparticles arises from reduced Cu–O bond strength and weakened electronic interactions between Cu and B-site elements. Meanwhile, the exsolved nanoparticles can improve gas adsorption via the charge density transfer from gas molecules to surface metal atoms. The present study establishes key mechanistic principles of nanoparticle exsolution and gas adsorption, informing the rational design of perovskite catalysts. A novel high-throughput screening strategy is also presented to accelerate the development of next-generation catalytic systems.</p>