Degradation of the electrochemical performance of LiFePO4 upon air exposure, assigned to a corrosion-type aging mechanism, implies the incorporation of hydroxyl groups and the formation of an amorphous tavorite-like phase at the surface. Using a carbon coating provides an efficient protection from this detrimental process but also modifies the surface in contact with the electrolyte. The formation and evolution of electrode/electrolyte interphases forming on both air-aged and carbon coated LiFePO4 are discussed based on combined quantitative 7Li, 19F MAS NMR, EIS and EELS measurements. Concerning the air-aged LiFePO4, the electrode/electrolyte interactions are dominated by the dissolution of the active material and an exacerbated reaction of incorporated hydroxyl groups with the electrolyte salt, resulting in a LiF rich interphase. This dissolution of the outer part of active material particles is accompanied by the departure of the previously formed interphase and a new interphase is then formed on a newly exposed surface. The resistive LiF rich interphase passivates the active material particles during cycling, forming a resistive film, hindering both Li ion transfer and material corrosion. Cellulose acetate based carbon coating prevents air-aging but yields to an accumulation of organic lithiated species, allowing Li transfer and maintaining good electrochemical performance.