To　date,　hydrogen　(H2)　therapy　has　received　widespread　attention.　However,　X-ray　triggered　sustainable　H2-producing　materials　with　controlled　release　for　cancer　treatment　have　not　been　reported.　Herein,　an　X-ray　triggered　sustainable　in　situ　H2　producing　platform,　Au　NR-TiO2@ZnS:Cu,Co-A(Au-TiO2@ZnS),　composed　of　Au-amorphous　TiO2　nano-dumbbell-shaped　heterostructure　coated　with　long　afterglow　particles,　was　developed　for　cancer　synergistic　H2-radiotherapy.　The　mechanism　of　H2　production　was　verified　by　theoretical　calculations　and　in　vitro　experiments.　Changes　in　the　apoptosis　pathway　caused　by　the　synergistic　effect　of　H2　and　radiotherapy　were　reported.　Guided　by　its　excellent　photoacoustic　imaging　capabilities,　mice　with　orthotopic　liver　cancer　achieved　excellent　therapeutic　effects　and　low　inflammatory　side　effects,　suggesting　that　Au-TiO2@ZnS　has　promising　application　potential　for　cancer　treatment　and　prognosis.　©　2021　Wiley-VCH　GmbH