We have rationally designed a new theranostic agent by coating near-infrared (NIR) light-absorbing polypyrrole (PPY) with poly(acrylic acid) (PAA), in which PAA acts as a nanoreactor and template, followed by growing small fluorescent silica nanoparticles (fSiO2 NPs) inside the PAA networks, resulting in the formation of polypyrrole@polyacrylic acid/fluorescent mesoporous silica (PPY@PAA/fmSiO2 ) core-shell NPs. Meanwhile, DOX-loaded PPY@PAA/fmSiO2 NPs as pH and NIR dual-sensitive drug delivery vehicles were employed for fluorescence imaging and chemo-photothermal synergetic therapy in vitro and in vivo. The results demonstrate that the PPY@PAA/fmSiO2 NPs show high in vivo tumor uptake by the enhanced permeability and retention (EPR) effect after intravenous injection as revealed by in vivo fluorescence imaging, which is very helpful for visualizing the location of the tumor. Moreover, the obtained NPs inhibit tumor growth (95.6 % of tumors were eliminated) because of the combination of chemo-photothermal therapy, which offers a synergistically improved therapeutic outcome compared with the use of either therapy alone. Therefore, the present study provides new insights into developing NIR and pH-stimuli responsive PPY-based multifunctional platform for cancer theranostics.