Red luminescent and superparamagnetic β-NaY0.8Eu0.2F4@γ-Fe2O3 nanoparticles, made of a 70 nm-sized β-NaY0.8Eu0.2F4 single crystal core decorated by a 10 nm-thick polycrystalline and discontinuous γ-Fe2O3 shell, have been synthesized by the polyol process. Functionalized with citrate ligands they show a good colloidal stability in water making them valuable for dual magnetic resonance and optical imaging or image-guided therapy. They exhibit a relatively high transverse relaxivity r2 = 42.3 mM−1·s−1 in water at 37 °C, for an applied static magnetic field of 1.41 T, close to the field of 1.5 T applied in clinics, as they exhibit a red emission by two-photon excited fluorescence microscopy. Finally, when brought into contact with healthy human foreskin fibroblast cells (BJH), for doses as high as 50 µg·mL−1 and incubation time as long as 72 h, they do not show evidence of any accurate cytotoxicity, highlighting their biomedical applicative potential.