A novel star-shaped polymer, porphyrin-poly(L-lysine) dendrons (PP-PLLD), is synthesized by the click reaction between azido-modified porphyrin and propargyl focal point poly(L-lysine) dendrons. Its chemical structure is characterized by 1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography (GPC) is analyses etc. Due to its amphiphilic property, the obtained PP-PLLD has a low critical micelle concentration in an aqueous solution, and can load doxorubicin (DOX) with a loading amount of 64 μg mg−1. By in vitro toxicity assay, PP-PLLD has no dark cytotoxicity but has significant phototoxicity. Moreover, DOX-loaded PP-PLLD shows a higher cytotoxicity under the light condition than PP-PLLD or DOX alone, suggesting PP-PLLD has a potential application in combined photodynamic therapy and chemotherapy.