The strong potential of platinum single atom(PtSA) in gas sensor technology is primarily attributed to its high atomic economy. Nevertheless, it is imperative to conduct further exploration to understand the impact of PtSAon the active sites. In this study,the evolution of PtSAon (100)CeO2and (111)CeO2 is examined, revealing notable disparities in the position and activity of surface PtSAon different crystal planes.The PtSAin (100)CeO2surfacecan enhancethe stability of Ce3+and construct a frustrated Lewis pair (FLP) to form a double active site by combining the steric hindrance effect of oxygen vacancies, whichincreases the response value from 1.8 to 27 and reducethe response-recovery time from 140-192s to 25-26s toward five ppm NO2at room temperature.Conversely,PtSAtends to bind to terminal oxygen on the surface of (111)CeO2and become an independent reaction site.The response valueofPtSA-(111)CeO2surface onlyincreased from 1.6 to 3.8.This research underscores the correlation between single atoms and crystal plane effects, laying the groundwork for designing and synthesizing ultra-stable and efficient gas sensors.