The structural properties of a mixture of ethylammonium nitrate (EAN), a protic ionic liquid, and lithium nitrate are explored using X-ray diffraction and reverse Monte Carlo simulation. The system is characterised by the amphiphilically driven polar-apolar domains segregation that is peculiar of EAN, whilst the lithium ions distribute in the charged domains where they undergo a further level of self-segregation, prompting for a new ion solvation mechanism in amphiphilically nanostructured ionic liquids.