Rational design of low‐cost and efficient transition‐metal catalysts for low‐temperature CO₂ activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO₂ methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO₂ catalyst affords an excellent low‐temperature performance hitherto, with a CO₂ conversion of 84.0 %, CH₄ selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g⁻¹ h⁻¹ for 106 h, reflecting one of the best CO₂ methanation performance to date on Ni‐based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re‐constructing monoclinic‐ZrO₂ supported Ni species with abundant oxygen vacancies can facilitate CO₂ activation, owing to the enhanced local electron density of Ni induced by the strong metal‐support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO₂ emission abatement and beyond.