We report structural and optical properties of Dy3+ doped Na0.5Bi0.5TiO3 (NBT), labeled as Dyx:NBT (x = 0.00–0.14). X-ray and neutron diffraction results of Dyx:NBT (x = 0.06 and 0.08) show the occupation of Dy3+ in both Bi and Ti-sites. Such behavior of a dopant ion occupying both in A and B-sites of ABO3 is called “amphotericity”. In conjunction with the above, Raman spectra show additional breathing vibrational (A1g) modes in the region of 700–900 cm−1. It confirms the asymmetry in TiO6 polyhedra and random distribution of Dy3+ and Ti4+ ions. Photoluminescence (PL) spectra show blue (484 nm; 4F9/2→6H15/2; magnetic dipole (MD) transition) and yellow (575 nm; 4F9/2→6H13/2; electric dipole (ED) transition) emissions. The asymmetric ratio (ED/MD) of emission transitions further confirms the amphoteric distribution of Dy3+ ions. Amphotericity and site-dependent luminescence variation show a strong correlation in structure-property relationships. © 2021