Dry　reforming　of　methane　(DRM)　has　been　investigated　for　more　than　a　century;　the　paramount　stumbling　block　in　its　industrial　application　is　the　inevitable　sintering　of　catalysts　and　excessive　carbon　emissions　at　high　temperatures.　However,　the　low-temperature　DRM　process　still　suffered　from　poor　reactivity　and　severe　catalyst　deactivation　from　coking.　Herein,　we　proposed　a　concept　that　highly　durable　DRM　could　be　achieved　at　low　temperatures　via　fabricating　the　active　site　integration　with　light　irradiation.　The　active　sites　with　Ni-O　coordination　(Ni-SA/CeO2)　and　Ni-Ni　coordination　(Ni-NP/CeO2)　on　CeO2,　respectively,　were　successfully　constructed　to　obtain　two　targeted　reaction　paths　that　produced　the　key　intermediate　(CH3O*)　for　anticoking　during　DRM.　In　particular,　the　operando　diffuse　reflectance　infrared　Fourier　transform　spectroscopy　coupling　with　steady-state　isotopic　transient　kinetic　analysis　(operando　DRIFTS-SSITKA)　was　utilized　and　successfully　tracked　the　anticoking　paths　during　the　DRM　process.　It　was　found　that　the　path　from　CH3*　to　CH3O*　over　Ni-SA/CeO2　was　the　key　path　for　anticoking.　Furthermore,　the　targeted　reaction　path　from　CH3*　to　CH3O*　was　reinforced　by　light　irradiation　during　the　DRM　process.　Hence,　the　Ni-SA/CeO2　catalyst　exhibits　excellent　stability　with　negligible　carbon　deposition　for　230　h　under　thermo-photo　catalytic　DRM　at　a　low　temperature　of　472　degrees　C,　while　Ni-NP/CeO2　shows　apparent　coke　deposition　behavior　after　0.5　h　in　solely　thermal-driven　DRM.　The　findings　are　vital　as　they　provide　critical　insights　into　the　simultaneous　achievement　of　low-temperature　and　anticoking　DRM　process　through　distinguishing　and　directionally　regulating　the　key　intermediate　species.