Electrodeposited Fe group: W and Mo alloys have the potential to replace hard Cr coatings for use in engineering applications where wear and corrosion resistance are needed. Electrochemical studies have concentrated in the past on Ni-W alloy deposition, but now interest in Co-W alloys has developed as they possess lower coefficients of friction when in contact with another metal. The most attractive coating composition is in the range 14-20 at.% W, if controlled deposition promotes crystalline alloys of high hardness, rather than softer amorphous alloys containing >20 at.% W. This paper employs ammonia free baths with low concentrations of cobalt and sodium tungstate and varying additions of sodium gluconate to produce alloys at close to 50% efficiency. Voltammetry, UV and visible spectrometry, and potentiostatic deposition have been performed on such baths, whilst XRD, SEM and TEM observations have been made on the deposits. This aims to optimise the process and to understanding the relationships between bath contents, electrochemical kinetics and alloy composition. Efficient deposition of coatings with hardness values up to 1000 kgf mm(-2) occurred from a bath containing a high concentration of gluconate. Such deposits arise from concentrations of Co-W-gluconate complexes which promote the formation of nanoscale alloy grains. Current densities up to 2.75 A dm(-2) in the agitated bath promoted deposition kinetics to form these highly orientated structures. These kinetics produced nano-segregation of W which may be assisted by the migration of Co-W clusters to boundary sites during the growth of the deposit. (C) 2010 Elsevier Ltd. All rights reserved.