In the present paper, we systematically studied the electrodeposition behaviors of iron, as well as the effects of overpotential and hydrogen bond donors on iron morphology in three deep eutectic solvents. It has found that the overpotential has no effect on iron morphology in DES1 and DES2. However, the overpotential plays an important role in shape evolution of iron deposited in DES3. In addition, this study shows that changing the hydrogen bond obviously affects the morphology of the iron deposited: The presence of urea hydrogen bond donor is conducive to the formation of film with flake network structure; and ethylene glycol hydrogen bond donor can facilitate the formation of quasi-sphere; while with the synergy of ethylene glycol and malonic acid, hollow nanospheres and yarn ball-like nanoparticles are beneficial to form.