Hyperbranched polyamidoamines(HPAs) were directly employed as macroinitiators to initiate the Sn(Oct)2 catalyzed ring-opening polymerization of ε-caprolactone(CL), resulting in multiarm star copolymers with poly(ε-caprolactone)(PCL) as shells and HPA as core(HPA-b-PCL). From 1H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could initiate the CL polymerization, and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the obtained stars were in the range of 115-353. Differential scanning calorimetry measurements demonstrated that the melting and crystallization temperatures, fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as the PCL arm length increased. HPAb-PCL stars could be used as nanocarriers to efficiently accommodate anionic dyes at acidic condition, while load cationic dyes at basic condition. Compared with the dye-loading behavior of multiarm star PCL with the neutral hyperbranched polyglycerol as core, it was deduced that HPA-b-PCL nanocarriers accommodated anionic dyes using the HPA core, while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyses also supported such deduction. Furthermore, HPA-b-PCL nanocarriers could selectively load the anionic Eosin Y or the cationic methylene blue from their mixture at p H = 6 or 9, respectively, realizing their separation. Hyperbranched polyamidoamines (HPAs) were directly employed as macroinitiators to trigger the ring opening polymerization of ε-caprolactone (CL), resulting in multiarm star copolymers with poly (ε-caprolactone) (PCL) as shells and HPA From 1H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could the CL polymerization, and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the stars were obtained in the range of 115-353. Differential scanning calorimetry measurements of the melting and crystallization temperatures, fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as PCL arm length increased. HPAb -PCL stars could be used nanocarriers not failing to accommodate anionic dyes at acidic condition, while loading cationic dyes at basic condition. Compared with the dye-loading behav ior of multiarm star PCL with the neutral hyperbranched polyglycerol as core, it was deduced that HPA-b-PCL nanocarriers hosted anionic dyes using the HPA core, while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyzes also supported such as that of HPA-b-PCL nanocarriers could load the anionic Eosin Y or the cationic methylene blue from their mixture at p H = 6 or 9, respectively, realizing their separation.