Mg1.5Al2O4.5:x% Eu3+ (0 ≤ x ≤ 2) nanopowders were successfully synthesized via sol–gel method. The X-ray diffraction (XRD) spectrum revealed that the Mg1.5Al2O4.5:x% Eu3+ matches the single phase of face-centred cubic MgAl2O4. The estimated average crystallite sizes calculated using the XRD spectra were found to be in the order of 4 nm. The estimated crystal size was confirmed by the high-resolution transmission electron microscopy. The energy dispersive X-ray spectroscopy confirmed the presence of all expected elementary composition (Mg, Al, O and Eu). The field emission gun scanning electron microscope showed that varying the Eu3+ concentration influence the morphology of the prepared nanophosphor. The photoluminescence results showed that the host emits the violet colour at around 382 nm, which was attributed to the defects within the band gap (Eg) of host material. The Eu3+-doped samples showed the emission at around 560, 580, 593, 618, 655 and 704 nm which are, respectively, attributed to the 5D1 → 7F3, 5D0 → 7F0, 5D0 → 7F1, 5D0 → 7F2, 5D0 → 7F3 and 5D0 → 7F4 characteristic transitions in Eu3+. The International Commission on Illumination colour chromaticity showed that the Eu3+ doping influences the emission colour.