The issue of neutron irradiation embrittlement of Reactor Pressure Vessel steels must be considered for Nuclear Power Plant life extension. This phenomenon partly arises from the existing interactions between dislocations and nanometric clusters composed of Cu, P, Si, Mn and Ni. The latter alloying element, playing a key role in the evolution of solute enriched clusters under irradiation, is the focus of this publication. To assess the effect of Ni on microstructure evolution under irradiation, particle accelerator based experiments were conducted. An under-saturated Fe3at.%Ni alloy was irradiated with self-ions, at 673 K, up to ∼1.2 dpa. Then, the microstructural damage was characterized, at the atomic scale, by conventional Transmission Electron Microscopy, Scanning Transmission Electron Microscopy coupled to Energy Dispersive X-ray Spectroscopy and Electron Energy Loss Spectroscopy, while chemical features were investigated by Atom Probe Tomography. Informations obtained by combining these coupled techniques provide evidence for the formation of a FCC phase, containing 25 at.%Ni, which can be either the disordered γ phase or the ordered L12 type Fe3Ni phase. The metastable or stable state of this FCC phase is discussed in the light of what is known from the literature. It is the first time that this BCC-FCC phase transformation is observed in an under-saturated α-FeNi alloy and this likely occurred via a Radiation Induced Precipitation (RIP) mechanism. Ni atom segregation is observed on cavities, dislocation lines and dislocation loops. The latter constitute nuclei for precipitates, leading to the formation of an additional segregation site for Ni: the precipitate FCC - matrix BCC nearly coherent interface. Similar mechanisms are argued to be operating also in high Ni RPV steels under neutron irradiation.