Divalent europium doped barium orthosilicate is a very important phosphor for the production of light emitting diodes (LEDs), generally associated to the green emission color of micron-sized crystals synthesized by means of solid-state reactions. This work presents the combustion synthesis as an energy and time-saving preparation method for very small nano-sized Ba2
particles, flexibly doped to acquire different emission energies. The size of the resulting spherical nanoparticles (NPs) of the green emitting Ba2
was estimated to about 35 nm applying the Scherrer equation and further characterized with aid of atomic force microscopy (AFM) as well as scanning electron microscopy (SEM). This phosphor is able to build homogeneous luminescent suspensions and was successfully down-sized without changing the optical properties in comparison to the bulk phosphors. Besides the X-ray diffraction (XRD) analysis and the different types of microscopy, the samples were characterized by luminescence spectroscopy. Undoped Ba2
NPs are not luminescent, but show characteristic red emission of the 5
= 0–4) electronic transitions when doped with Eu3+
ions. Moreover, these orthosilicate nanoparticles generate blue light at low temperatures due to impurity-trapped excitons, introduced by the partial substitution of the Ba2+
ions in the Ba2
lattice causing a substantial distortion. A model for the temperature behavior of the defect luminescence as well as for their nature is provided, based on temperature-dependent luminescence spectra and lifetime measurements.