Al1-xWx (x=0.1, 0.2, 0.5, 0.9) powders have been prepared by mechanical alloying of the elements in a planetary ball mill. The structure and morphology of the milled powders were investigated using X-ray diffraction and electron microscopy. The solubility of Al in W is greatly extended, even more than 50%. The results are analyzed using embedded atom method (EAM) according to the scheme of mechanical alloying extending solid solubility. The theoretical results are in good agreement with the experimental.