The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C(4)mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation-growth kinetics. Analysis of chronoamperometric data indicated that the nucleation-growth mechanism is instantaneous at all potentials in the case of [BMIM][BF4] and [C(4)mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C(4)mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction. (C) 2011 Elsevier Ltd. All rights reserved.