A series of La1−xAlO3: xEu3+ (x = 0, 2, 4, 6 and 8 mol%) nanophosphors have been synthesized by a hydrothermal technique and were investigated by an X-ray powder diffractometer, field emission scanning electron microscopy, high-resolution transmission electron microscopy and fourier transform infrared spectroscopy. Further, photoluminescent studies have also been orderly explored under the near-ultraviolet light excitation. When excited with 395 nm, the Eu3+: LaAlO3 nanophosphors emission peaks observed at 579, 591, 620, 649 and 700 nm due to the 5D0→7Fj (J = 0–4) transitions of Eu3+ ions. The prominent emission peak was perceived at 620 nm, which associated to the 5D0→7F2 hypersensitive transition of Eu3+ ion. The optimum doping concentration of Eu3+ in LaAlO3 host is around 6 mol% and the concentration quenching effect is through the dipole–dipole interaction. The Commission International de I’Eclairage (CIE) color co-ordinates were determined from emission spectra and the values (x, y) were closer to National Television Standard Committee typical value of red emission. As an outcome, the prepared nanophosphors are highly suitable for red component of white light emitting devices.