<p>The development of efficient catalysts for CO₂ hydrogenation to methanol is highly urgent but is hindered by maintaining precise control over intermediate transfer. Here we demonstrate that the oxidized 2D 1 T′-MoS₂ uniquely integrates both CO₂ activation and selective hydrogenation functions within a single material through its inherent 2D structural merit. The singular S-edge structure of 1 T′-MoS₂ creates a uniform catalytic landscape where in-plane O-substituted sulfur defects and oxidized edges operate in concert. This spatially organized system achieves CO₂ conversion of 23.0% with a methanol selectivity of 99.2% and the specific reaction rate reaches 0.91 ± 0.01 g_methanol/g_cat/h at 210 °C. We reveal the complete reaction trajectory: (i) preferential CO₂ dissociation at in-plane sites generates weakly adsorbed *CO intermediates that (ii) undergo directed desorption-retrapping to edge sites where (iii) the oxidized edge of 1 T′ phase uniquely stabilizes the C-O bond during hydrogenation. This work establishes the phase-engineered 1 T′-MoS₂ as a paradigm for single-material tandem catalysis to demonstrate how the spatially coupled active sites boost the CO₂ hydrogenation.</p>