Single-atom catalysts (SACs) have attracted significant attention because they exhibit unique catalytic performance due to their ideal structure. However, maintaining atomically dispersed metal under high temperature, while achieving high catalytic activity remains a formidable challenge. In this work, we stabilize single platinum atoms within sub-nanometer surface cavities in well-defined 12CaO·7Al₂O₃ (C12A7) crystals through theoretical prediction and experimental process. This approach utilizes the interaction of isolated metal anions with the positively charged surface cavities of C12A7, which allows for severe reduction conditions up to 600 °C. The resulting catalyst is stable and highly active toward the selective hydrogenation of nitroarenes with a much higher turnover frequency (up to 25772 h⁻¹) than well-studied Pt-based catalysts. The high activity and selectivity result from the formation of stable trapped single Pt atoms, which leads to heterolytic cleavage of hydrogen molecules in a reaction that involves the nitro group being selectively adsorbed on C12A7 surface.