Digestion is an important process, the first one in the conversion of food to energy. From this angle, digestion of nutrients was extensively studied, and this process was found to be very efficient. Nevertheless, many molecules contained in food do not bring energy but are essential as they allow maintaining normal body functions. These are the micro-nutrients, including vitamins and minerals. On top of that, recent nutrition research identified many other bioactive molecules (termed micro-constituents as they only represent a small part of the food) playing a role in the health status, e.g. contributing to the prevention of chronic diseases. However, it was shown that their digestion is much less efficient, especially that of lipophilic micro-constituents (such as lipophilic vitamins, carotenoids, cholesterol and other steroids) depending on food structure and composition. Enhancing their health effects through optimal absorption and bioavailability thus requires a comprehensive knowledge of their release from food within the gastrointestinal tract. To study this step, of which the endpoint is termed bioaccessibility, in vitro digestion methods proved to be well adapted to fundamental research. This review reports the effects of the physicochemical parameters controlling the bioaccessibility of various lipophilic micro-constituents from emulsion. Notably, it appears that this bioaccessibility is related to the bioaccessibility of lipid nutrients, as their kinetics are interrelated. This knowledge will enable the formulation of food in terms of structure and composition to obtain optimal bioaccessibility. As the latter likely controls bioavailability, prevention of some metabolic disorders could be targeted in the long term.