Polymer vesicles prepared by self-assembly techniques have attracted increasing scientific interest in recent years. This is as a result of their numerous potential applications such as tunable delivery vehicles, for the templating of biomineralization, as nanoreactors and as scaffolds for biological conjugation. Presented in this review are the recent advances in the preparation and application of ‘smart’ and functional block copolymer vesicles such as those which respond to external stimuli to afford a change in structure, morphology or controlled release event. In this Highlight, we first give an overview of the structure of polymer vesicles, followed by a summary of the methods used for their preparation. We then focus on recently developed intelligent polymer vesicles which can respond to the application of external stimuli such as a change in temperature, pH or redox to afford novel nanomaterials. The potential applications of these materials are explored with specific focus on the functionalization of various domains of the polymer vesicles. Finally, the current limitations in the preparation and application of polymer vesicles are explored as are the challenges facing the development of these nanostructures towards real-world applications.