Controlled loading more than one active cargos on metal–organic frameworks (MOFs) and keeping monodispersity have long been a great challenge due to easy agglomeration and collapse of MOFs in water. Herein, we develop an emerging self-stablized double enzyme delivering system with long-time monodispersion, and achieve synergistic cancer starvation and photothermal therapy (PTT) without any chemotherapeutics. Loading of glucose oxidase (GOx) confers strong coordination interactions with MOFs, which not only endows robust self-stablized monodispersion without any surface modification, but also guarantees uniform deposition of GOx-like nanoenzyme of Au nanoparticles with catalytic and photothermal conversion property. Our design establishes an effective synergistic therapy platform to generate reactive oxygen species, decreases mitochondrial membrane potential, and induces cell apoptosis. Immunofluorescence study confirms activation of Caspase 3 of apoptosis pathway, and significantly inhibits proliferation of cancer cells. This work provides new insight into stabilizing MOFs by GOx without any chemical modifications, and constructs an unprecedented double enzyme delivering system with excellent in vivo and in vitro cancer synergistic therapy effect at very low doses without using any chemotherapeutic drugs.