Tungsten carbide has been synthesized directly by ball-milling tungsten powder and activated carbon in vacuum. The structural development of the WC phase with milling times up to 310 h has been followed using X-ray, neutron diffraction and scanning electron microscopy. Subsequent annealing (at 1000 degrees C for 1 and 20 h) of material milled for 90 h or longer, results in samples comprising almost entirely crystalline WC. The production of WC itself during milling results in enhanced iron contamination from the steel mill and balls on extended milling which were monitored by energy-dispersive X-ray and Mossbauer spectroscopies.