Vesicles are representative mimic systems for natural lipid membranes. Th is chapter summarizes recent research in the area of synthesis of vesicular structures from self-assembly of lipids, polymers, and small molecules in solutions and synthesis of hard vesicles by using vesicles as templates, like hollow silica spheres. Th en we provide an overview of the characterization tools of structures by microscopic and scattering method. Th e present study will focus on the discussion about the various types of self-assembled smart vesicles, which are revealed by their capability to respond to external stimuli such as temperature, pH, and others. In addition, the application of these smart vesicles toward molecular separation, chemical sensors, nanoreactors and microreactors, catalysts, and drug delivery vehicles are described.