A hyperbranched-linear-hyperbranched amphiphile (HLHA) consisting of polyglycerol, polycaprolactone and polycitric acid blocks was synthesized and characterized. The self-assembly of HLHA in aqueous solutions produced nearly monodispersed nanoparticles. The average size of the nanoparticles in aqueous solutions was 120 nm. Spectroscopy and microscopy analysis showed that the nanoparticles change their structure in response to changes in the polarity of the medium in the solution state, so that the hydrophobicity or hydrophilicity of the solvent dominates the structure and properties of the nanoparticles. This property was used to load hydrophobic anticancer drugs inside the nanoparticles and also to deliver them to cancer cells successfully. In addition to the mentioned properties, the efficient uptake and low toxicity enable the prepared nanoparticles to be potential new systems for future cancer therapy.