Among W alloys, Fe-W has seen much attention recently, due to the need of moving toward the design of environmentally friendly materials. Coatings with 4, 16 and 24 at.% of W were electrodeposited from an environmental friendly Fe(III)-based glycolate-citrate bath. The samples were annealed in vacuum at different temperatures up to 800 °C. Different crystalline phases are formed upon annealing: α-Fe, Fe2W, Fe3W3C, Fe6W6C, and FeWO4. Their grain size and distribution within the coating was studied by means of Electron Backscattered Diffraction (EBSD) technique. The effect of annealing on the mechanical properties of the coatings was analyzed performing nanoindentation measurements. The results show a considerable increase of the hardness followed by a rapid decrease at higher temperatures. The highest hardness value, i.e. 16.5 GPa, is measured for the sample with 24 at.% of W after annealing at 600 °C owing to the precipitation of α-Fe crystallites. This study indicates the possibility to substantially increase the hardness of electrodeposited Fe-W coatings by optimization of the annealing treatment. In addition, the critical influence of the carbide and oxide phases on the mechanical properties of alloys is discussed. Hence, Fe-W coatings rich in W can be applied as a possible candidate for protective coating applications at elevated temperatures.