A substitute for propionic acid, which is a complexing agent in the Ni W electrodeposition process for producing bulk nanocrystalline alloys with high ductility, was explored. Bulk nanocrystalline Ni W alloys were electrodeposited using electrolyte that primarily consisted of nickel sulfamate and sodium tungstate with sodium propionate and/or sodium gluconate. Their W content, impurity contents, microstructure, and mechanical properties were investigated. The Ni W alloys electrodeposited from conventional bath exhibited tensile strength of 1.66 GPa and elongation of 6.5. Substitution of propionic acid by sodium propionate enhanced tensile elongation up to 11.3 along with high strength of 1.65 GPa. Also, substitution by sodium gluconate enhanced tensile strength up to 1.80 GPa with elongation of 5.2. The results of this study demonstrate that the propionic acid in the Ni W electrodeposition process can be replaced by sodium propionate without property degradation.