Plate-like Na2W4O13 crystals having sizes of up to 35 x 7mm and thicknesses of 0.7 mm were grown from Na2O-WO3 high-temperature solutions. The crystal growth was conducted by heating a mixture at 1100 degreesC for 10h, and then cooling to 500 degreesC at a rate of 5 degreesC/h. The crystals obtained were colorless and transparent. The most suitable composition of the solution was Na2O(30 mol%)-WO3(70 mol%). The indices of the well-developed faces were {1 0 0}. The Na2W4O13 crystals emitted a luminescence band at 2.33 eV, when they were excited at 10K with photons in the fundamental absorption region (> 3.75 eV). This green luminescence was thermally quenched above 200 K, with an activation energy of 0.22 eV.