IR, Raman, X-ray, electron absorption and luminescence studies have been performed for novel laser Nd 3 BWO 9 and Eu 3 BWO 9 borotungstates exhibiting non-centrosymmetric crystal structures. The assignment of observed vibrational modes to respective symmetry and vibrations of atoms has been proposed. These studies have shown that vibrational and electronic properties of these crystals can be better explained when P6 3 symmetry is assumed, instead of previously proposed P3 one. The crystal structure refinement has also confirmed that symmetry of the Eu 3 BWO 9 borotungstates is P6 3 , not P3.