Near-infrared-(NIR)-light-triggered photothermal nanocarriers have attracted much attention for the construction of more smart and effective therapeutic platforms in nanomedicine. Here, a multifunctional drug carrier based on a low cost, natural, and biocompatible material, bamboo charcoal nanoparticles (BCNPs), which are prepared by the pyrolysis of bamboo followed by physical grinding and ultrasonication is reported. The as-prepared BCNPs with porous structure possess not only large surface areas for drug loading but also an efficient photothermal effect, making them become both a suitable drug carrier and photothermal agent for cancer therapy. After loading doxorubicin (DOX) into the BCNPs, the resulting DOX-BCNPs enhance drug potency and more importantly can overcome the drug resistance of DOX in a MCF-7 cancer cell model by significantly increasing cellular uptake while remarkably decreasing drug efflux. The in vivo synergistic effect of combining chemotherapy and photothermal therapy in this drug delivery system is also demonstrated. In addition, the BCNPs enhance optoacoustic imaging contrast due to their high NIR absorbance. Collectively, it is demonstrated that the BCNP drug delivery system constitutes a promising and effective nanocarrier for simultaneous bioimaging and chemo-photothermal synergistic therapy of cancer.