The electrochemical behavior of electrodeposited nickel and Ni-W nanostructured alloys is discussed by studying the polarization curves in acidic medium. As tungsten content varies, several metallurgical parameters that can influence the electrochemical behavior are also modified, namely grain size, nature of grain boundaries, crystallographic texture and light element contamination. Comparing the behavior of Ni-W coatings with that of pure nickel and annealed coatings highlights that tungsten incorporation enhances anodic dissolution and has a detrimental influence on passive film, whereas grain size and grain boundary character behave as second-order parameters. (C) 2016 Elsevier B.V. All rights reserved.