A tri-layered nanofibrous hydrogel thin film with temperature sensitivity is introduced as a new controlled drug release system to treat breast cancer. A simultaneous heat generation with the tunable release of dual drugs is observed in response to visible light radiation. A tri-layered nanofibrous sheet was fabricated through sequential electrospinning the blends of Au@Chit@DOX-loaded poly(N-isopropylacrylamide-co-N-methylol acrylamide) (poly (NIPAAm-co-NMA)) and Curcumin-loaded poly (vinyl alcohol) (Cu-loaded PVA), where the Cu-loaded PVA nanofibers (NFs) are sandwiched between two layers of Au@Chit@DOX-loaded poly (NIPAAm-co-NMA) NFs. After thermal crosslinking of the tri-layered nanofibrous sheet, the nanofibrous hydrogel thin film is obtained. FTIR/ATR, UV–Vis, Photoluminescence, and PXRD analyses were used for characterizing. PVA NFs and poly (NIPAAm-co-NMA) NFs were observed in the average diameters of 358 and 212 nm, respectively, and Au@Chit@DOX nanoparticles (NPs) appeared as local thickening inside the NFs. The distribution of drugs was visualized with confocal images. The thermal stability up to 295 °C and tensile strength of 0.65 MPa with 99.36% elongation were reported for the nanofibrous hydrogel thin film. Unlike the fast release of drugs from the nanofibrous sheet, a controlled release of drugs was observed from the nanofibrous hydrogel thin film at 45 °C and under visible light radiation. 52% at 45 °C and 55% under light radiation were reported for the Cur release and 86% at 45 °C and 88% under light radiation were observed for the release of DOX within 18 h. The in vitro cell viability results under light radiation displayed a chemo-thermal therapy over breast cancer cells.