Developing a spatiotemporal-controlled platform with feasible synthesis and multifunctionality is highly desirable in the field of nanomedicine. Here, we present a near-infrared (NIR)-light-triggered approach to control the supramolecular assembly system for drug release and achieve synergistic chemo-photothermal therapy for cancer. A cucurbit[7]uril (CB[7]) stabilized gold nanostar (GNS) platform is designed to encapsulate the anticancer drug camptothecin (CPT) via host-guest chemistry. Importantly, CB[7] behaves not only as a surfactant to improve the stability of GNS in the aqueous solution but also as the cage for intermolecular assembly of CPT molecules. Moreover, without the competitive complexation, the drug release could be stimulated under NIR light irradiation. Synergistic treatment of cancer can be achieved by combining chemotherapy with the photothermal effect of GNS. This work develops a NIR-light-triggered cucurbituril-based drug-release approach that opens the door for remote control of drug release in the supramolecular assembly system.