X-ray　photoelectron　spectroscopy　(XPS)　is　a　crucial　surface　analysis　technique　that　has　become　a　key　tool　in　the　study　of　heterogeneous　catalysis.　Detecting　surface　chemistry　under　conditions　that　closely　mimic　actual　industrial　catalytic　processes　is　essential　for　understanding　the　mechanisms　involved.　In　the　past　decade,　near　ambient　pressure　X-ray　photoelectron　spectroscopy　(NAP-XPS)　has　been　increasingly　utilized　to　study　the　surface　chemistry　of　catalysts　during　heterogeneous　catalytic　processes,　offering　insights　into　structure-performance　correlations.　This　review　begins　with　a　brief　overview　of　NAP-XPS　instrumentation.　Next,　we　discuss　the　application　of　NAP-XPS　in　the　study　of　thermal　catalysis　reactions,　followed　by　a　summary　of　the　research　on　catalyst　restructuring　under　reaction　conditions.　Additionally,　we　address　the　challenges　and　future　perspectives　for　the　development　and　application　of　NAP-XPS.　Catalysis　is　inherently　dynamic,　requiring　an　understanding　of　the　real-time　behavior　of　catalysts　under　varying　conditions.　Therefore,　future　improvements　in　the　ability　to　probe　reaction　intermediates　with　higher　spatial　and　temporal　resolution　under　conditions　that　closely　mimic　industrial　environments　are　needed.　©　Science　China　Press　2025.