In recent years various polymeric vesicles have been reported that show promising results for drug delivery applications, nanomotors and/or nanoreactors. These polymeric vesicles can be assembled from many different materials and various coupling reactions have been applied for functionalization of the vesicles. However, the designs reported are still rather simple, as it is challenging to mimic biological complex systems. In this review we focus on the properties of widely used hydrophobic polymers to better understand polymersome properties for various applications. Examples are shown of how researchers have used and modulated block-copolymers and their properties to their advantage. Furthermore, an overview of possible end group functionalizations of nanoparticles is reported, giving insight in recent developments of smart nanoparticles for biomedical applications.