Octahedral indium particles are electrodeposited on the molybdenum films from 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim][TfO]) ionic liquid. Chronoamperometry and SEM images demonstrate that the nucleation of indium on the glassy carbon electrode involves an instantaneous process. Molecular dynamic simulation reveals the interaction between [Bmim](+) and [TfO](-) ion pairs and the indium surfaces, which can explain the formation of polyhedral shapes of the particles. (C) 2016 The Electrochemical Society. All rights reserved.