Polymersomes are widely used as drug delivery system however they have shortcomings in drug-eluting properties that are attributable to the high molecular weight of the copolymers forming their membrane. Here we demonstrate for the first time how novel class of polymersomes from very short, liquid to soft star-shaped copolymers can be empowered to form an efficient drug delivery system. The copolymers undergo self-assembly in water into a stable, nano-sized rod or a spherical shape polymersomes. Increasing the Mw of the hydrophobic moieties the CMC value is decreased accompanied with the tendency to form a more spherical structure. The poorly water-soluble anticancer drug camptothecin was loaded into the fabricated polymersomes, resulting in a high drug loading content, and released over a period of 7 days. Furthermore, this biocompatible system could deliver a variety of drugs intracellularly in a rapid yet controlled manner. Therefore, this nano system’s tailorable properties, biocompatibility and ability to incorporate hydrophobic drugs and release them intracellularly are desirable traits for anti-cancer delivery system and other biomedical applications.