AbstractGdFeO₃ perovskite attracted large interest in different fields thanks to peculiar magnetic and optical properties that are further tunable by means of doping processes and achievable on both Gd and Fe sites or by properly choosing the synthesis routes. In this paper, nanometric GdFeO₃ compounds, undoped and doped with diamagnetic Ca²⁺ and Mg²⁺ ions, were synthesized by microwave assisted, sol–gel, and polyol syntheses and characterized by X-ray diffraction, showing solid solutions formation. Raman spectroscopy allowed us to confirm, from peak enlargements, the Ca and Mg substitution on Gd and Fe sites, respectively. The magnetic data showed the presence of magnetic domains as consequence of doping with diamagnetic ions, which seem to play a crucial role in the magnetic activity of the compounds. A superparamagnetic behaviour is evidenced; nevertheless, its intrinsic character is not definitely demonstrated. Indeed, the possible presence of traces of magnetic impurities, which are easily obtainable in these samples, such as iron oxides, must be taken into account.