Polyion complex (PIC) formation is one of the most powerful techniques for obtaining molecular self-assemblies in aqueous media, and useful for material syntheses particularly in the biomedical field. In this review article, recent progress on PIC vesicles (PICsomes) is summarized. PICsomes are characterized by their simple preparation, semipermeability and environment-sensitivity. Very recently, the methods to control structural uniformity and size of the vesicles have been established, and the potential utility of PICsomes has been expanded by crosslinking their PIC layers. In addition, the unique dynamic nature of PICs is also described.