<p>The catalytic conversion of CO₂ into value-added chemicals via the reverse water-gas shift (RWGS) reaction represents a significant pathway for mitigating climate change and enabling sustainable carbon utilization. However, Pt-based catalysts, despite their superior H₂ activation ability, often suffer from inadequate CO selectivity and durability under high-temperature conditions, primarily due to excessive CO adsorption at low-coordinated Pt edge sites. Herein, we present a sulfur (S)-mediated targeted passivation strategy to engineer Pt-CeO₂ catalysts with atomically tailored active sites, effectively addressing the critical activity-stability-selectivity trade-off. The incorporation of S into CeO₂ support induced optimized electronic modulation, as evidenced by in situ/ex situ characterizations and density functional theory (DFT) calculations, which weakened *CO adsorption strength and suppressed the methanation pathway. The optimized Pt-S-CeO₂ catalyst exhibits remarkable performance at 600 °C: CO selectivity &gt;95%, CO production rate of 8.8×10⁻⁵mol g_cat⁻¹ s⁻¹, and &lt;10% activity loss over 250 h. On the other hand, this work establishes a framework for targeted dopant-mediated site engineering in heterogeneous catalysis, offering a generalizable route to reconcile conflicting performance in CO₂ hydrogenation systems and beyond.</p>