The direct hydrogenation of 2‐nitroacylbenzene to 2,1‐benzisoxazole presents a significant challenge in the pharmaceutical and fine chemicals industries. In this study, a defect engineering strategy is employed to create bifunctional single‐atom catalysts (SACs) by anchoring Pt single atoms onto metal vacancies within MgO(Al) nanosheets. The resultant Pt1/MgO(Al) SAC displays an exceptional catalytic activity and selectivity in the hydrogenation‐cyclization of 2‐nitroacylbenzene, achieving a 97.5 % yield at complete conversion and a record‐breaking turnover frequency of 458.8 h−1 under the mild conditions. The synergistic catalysis between the fully exposed single‐atom Pt sites within a unique Pt‐O−Mg/Al moiety and the abundant basic sites of the MgO(Al) support is responsible for this outstanding catalytic performance. The current work, therefore, paves the way for developing bifunctional or multifunctional SACs that can enhance efficient organocatalytic conversions.