The Ba2Na3[B3O6](2)F single crystals of optical quality were grown. Raman, optical absorption and luminescence spectra of pure and neodymium-doped Ba2Na3[B3O6](2)F crystals were studied. Besides a broad band emission near 330 nm associated with native defects, the features related to 4f(3)-> 4f(3) transitions in the Nd3+ ions were found both in absorption and luminescence. Ba2+ replacement by Nd3+ ion in the Ba2Na3[B3O6](2)F lattice was established to reduce the symmetry of oxygen surrounding. Na presence in the structure was found to facilitate the Rare Earth impurity incorporation, supposedly because of Na-assisted charge compensation. (C) 2014 Elsevier By. All rights reserved.