AuFe electrodeposits onto a rotating disk electrode were examined to assess the composition and current efficiency behavior when citric acid, ascorbic acid, or a combination of both is present in the electrolyte. Nanowires were subsequently fabricated with pulsed current deposition to create compositionally, multilayered Au/FeAu nanowires. The FeAu layer of the nanowires was porous in a citrate electrolyte, but the porosity decreased with the addition of ascorbic acid in the electrolyte. Comparatively higher side reaction partial current densities (i(sr)) in the citric acid electrolyte generated local alkaline conditions, inducing the chemical precipitation of Fe ions in the form of iron oxide nanoparticles inside the recess, which manifested as the regions of high porosity. Nonporous layers observed in the ascorbic acid bath, in combination with decreased i(sr) and increased current efficiency of the deposits, suggested that a similar mechanism of Fe precipitation inside the nanorecess is less likely. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3409843] All rights reserved.