K[AsW2O9], prepared by high-temperature solid-state reaction, is the first member of the arsenate-tungsten bronze family. The structure of K[AsW2O9] is based on a 3-dimensional (3D) oxotungstate-arsenate framework with the non-centrosymmetric P2(1)2(1)2(1) space group, a=4.9747(3) angstrom, b=9.1780(8) angstrom, c = 16.681(2) angstrom. The material was characterized using X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Raman and infrared (IR) spectroscopic techniques. The results of DSC demonstrate that this phase is stable up to 1076 K. Second harmonic generation (SHG) measurements performed on a powder sample demonstrate noticeable (0.1 of LiIO3) non-linear optical (NLO) activity. (C) 2013 Elsevier Inc. All rights reserved.