Austenitic 316L stainless steel alloys annealed at 550°C for 100 h present a few ferrite precipitates surrounded by a new interfacial phase, here called the I-phase, that develops at the level of the austenite/ferrite interface. The I-phase presents the typical patterns of an icosahedral quasicrystal with a primitive hypercubic lattice of parameter A = 0.63 nm. The marked orientation relationships between the I-phase and the ferrite precipitates strongly suggest that this phase results from a decomposition of the ferrite and not of the austenite. The I-phase is metastable and transforms eventually after annealing at 700°C to the stable crystalline σ-phase.