Star-shaped porphyrin-cored poly(L-lactide) (SPPLLA) was synthesized using a tetra-hydroxyethyl terminated porphyrin as a core initiator and 4-(Dimethylamino)pyridine (DMAP) as a catalyst in THF at 50 °C. The molecular weight of as-synthesized polymer were measured by GPC and1HNMR. It was found that the molecular weight of SPPLLA could be adjusted linearly by controlling the molar ratio of L-lactide to porphyrin core initiator, and the molecular weight distribution was reasonably narrow. Furthermore, SPPLLA polymers showed similar UV-vis spectra compared with porphyrin core initiator. Consequently, this will provide potentially porphyrin-cored poly(L-lactide) for photodynamic therapy.