The bulk crystals of LiTm(WO 4 ) 2 with dimensions up to 10 × 15 × 3 mm have been obtained for the first time. Crystals of the compound melts congruently at 1007 °C, however melt crystallization of high quality crystal is impossible due to phase transition at ∼920 °C. The top seeded solution method from Li 2 WO 4 -WO 3 flux was successfully applied reducing the growth temperature below 900 °C. According to single crystal x-ray measurements, the crystal corresponds to the P2/n space group. Raman, luminescence and transmission spectra reveal optical features owing to the presence of thulium ions, and therefore the materials could be further studied in the scope of laser and luminescence applications.