A locally administered combination of chemotherapy and photothermal therapy may be suitable for the treatment of cervical cancer. In this study, doxorubicin (DOX) and indocyanine green (ICG) co-loaded mesoporous silica nanoparticles (DIMSN) were prepared. Then the nanoparticles were incorporated into chitosan/poly(vinyl alcohol) (CS/PVA) to form multifunctional composite nanofibers (DIMSN/F) via the electrospinning process. Under the mimic erosion of vaginal secretion, DIMSN/F presented site-specific drug release while the local delivery of a thermosensitive DIMSN-loaded gel (DIMSN/gel) failed in doing so. The vaginal implantation of DIMSN/F could achieve maximized drug accumulation in the vagina of mice compared to the systematic injection of DIMSN. Finally, the photothermalchemotherapy (PTCT) effects of DIMSN/F were studied in both subcutaneous and orthotopic cervical cancer models in mice but drug penetration in the hard nodular tumor posed a great challenge. For all this, the tumor inhibition rate (TIR) for orthotopic cervical/vaginal cancer was still as high as 72.5%, presenting its great potential for the treatment of cervical cancer.