W1-xAlxC (x = 0.33, 0.50, 0.75, 0.86) solid solutions have been synthesized directly by ball-milling tungsten powder, aluminum powder and activated carbon. The structural development of W0.5Al0.5C phase with the milling times up to 160 h has been followed using X-ray diffraction. X-ray photoelectron spectra demonstrate that Al atom takes the place of W. High temperature annealing experiment reveals that Al is stable in hexagonal structure to 1873 K. Transmission electron microscopy image shows that the grain size of the prepared powders is about 5 nm. (C) 2004 Elsevier Ltd. All rights reserved.