Illustration of the synchronous chemoradiation. The co-assembly of hydrophobic Au-LAHP NPs, oxidation-responsive PPS-PEG amphiphilic polymers, and hydrophilic DOX result in Au-LAHP-vDOX vesicles. Upon irradiation, the in situ formation of •OH triggers oxidation of PPS from hydrophobic to hydrophilic, leading to degradation of the vesicles and burst release of cargo drugs. Therefore, drug release is synchronously confined when irradiation is applied in a spatiotemporally controllable manner.