Summary Emulsifiers are often used in the food industry to stabilize interfaces in emulsions and foams, for example. When added to an aqueous phase, emulsifiers form spontaneously self-assembly structures. Such structured fluids can be used for active ingredients encapsulation or as micro-reactors for flavour formation. In the present paper we describe the potentialities of DSC, mainly micro-DSC, to study phase transitions of emulsifiers alone and with addition of water. The main role of the calorimetric techniques will probably be to precisely determine melting and crystallization zones, to inform about polymorphism and hysteresis due to undercooling, and especially to follow the effects of guest molecules on the weak liquid crystal transitions. Micro-DSC, when compared to other techniques, generally allows measurements over an extended temperature range.