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Herein, a metal\u2010phenolic nanosensitizer (Hf\u2010PSP\u2010DTC@PLX) was integrated via an acid\u2010sensitive hydrogen sulfide (H<jats:sub>2<\/jats:sub>S) donor (polyethylene glycol\u2010co\u2010polydithiocarbamates, PEG\u2010DTC) and a hafnium\u2010chelated polyphenolic semiconducting polymer (Hf\u2010PSP) in an amphiphilic polymer (poloxamer F127, PLX). Hf\u2010PSP\u2010DTC@PLX elicited a high imaging performance for precise RT and generated H<jats:sub>2<\/jats:sub>S to reduce the cellular oxygen consumption rate via mitochondrial respiration inhibition, which reprogrammed the oxygen metabolism for improvement of the tumor oxygenation. Then, Hf\u2010sensitization could fully utilize the well\u2010preserved oxygen to intensify RT efficacy and activate immunogenicity. 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