X-ray absorption near edge structure (XANES) spectra have been collected for 1-alkyl-3-methylimidazolium bromide [C(n)mim]Br ILs with different alkyl chains (n = 2, 4). The XANES technique has been found to be sensitive to the subtle differences in the Br coordination environment present in [C(2)mim]Br and [C(4)mim]Br ILs, that are solid at room temperature. With this Letter we show that XANES is a new effective tool for studying the local structural arrangements around selected atoms in ILs both in the solid and liquid phase. (C) 2013 Elsevier B.V. All rights reserved.