In recent years, ductile amorphous and nanocrystalline M-W (M=Fe, Ni) alloys were produced by electrodeposition. The structural studies of these alloys were carried out by using EXAFS, SAXS and Mossbauer spectroscopic methods. The mechanical alloying was also done for the alloys of same composition as the alloy made by electrodeposition. The crystal structure of the electrodeposited Ni-W alloy was similar to that of Ni4W phase. The nearest Ni-Ni distance was determined to be 2.49 Angstrom, Ni-W distance was determined to be 2.50 Angstrom. The average crystal grain size of the as-electrodeposited Ni-W alloy was estimated about 2.5 nm from Guinier plot of SAXS spectra. The as electrodeposited Fe-21.6 at. % W alloy has short range order, but not any medium range order around Fe and W atoms, it possesses amorphous structure. The nearest Fe-Fe and Fe-W distances in the alloy were determined to be 2.42 Angstrom and 2.53 Angstrom respectively. The structure of mechanically alloyed. M-W (M=Fe, Ni) alloys are similar to that of the as electrodeposited M-W (M=Fe, Ni) alloys. But these alloys include a small amount of undissolved pure Fe, Ni and W, also.