Multi‐wall carbon nanotubes (MWCNTs) produced by the arc discharge between two graphite rods in liquid nitrogen have been investigated with the use of Raman spectroscopy and transmission electron microscopy (TEM). The effects of the applied voltage on the structural properties of the produced MWCNTs have been observed, in particular, as it concerns the size of the innermost and outermost diameters. The apparent discrepancies observed between the Raman and TEM results are explained through the observation of a selective response of the MWCNTs to the excitation laser energy in Raman spectroscopy, similar to the case of single‐wall CNTs. Electronic structure calculations correlate such behavior with optical transitions, in the presence of strong electronic localizations, spatially confined in a few neighboring walls. Copyright © 2011 John Wiley & Sons, Ltd.