Microfluidics enables the precise manipulation of droplets to form emulsions in a controlled manner and provides an ideal platform for formulating uniform structures with high encapsulation efficiency. We describe some novel structures that we engineer using controlled emulsions as templates for directing the assembly of amphiphiles. We also show examples of how further assembly can be achieved by using these amphiphiles sitting at liquid-liquid as templates at another level. This template-directed approach is a promising and versatile route towards generating encapsulation structures with tunable release properties.