El'gygytgyn (Chukotka, Arctic Russia) is a well-preserved impact structure, mostly excavated in siliceous volcanic rocks. For this reason, the El'gygytgyn structure has been investigated in recent years and drilled in 2009 in the framework of an ICDP (International Continental Scientific Drilling Program) project. The target rocks mostly consist of rhyodacitic ignimbrites and tuffs, which make it difficult to distinguish impact melt clasts from fragments of unshocked target rock within the impact breccia. Several chemical and petrologic attempts, other than dating individual clasts, have been considered to distinguish impact melt from unshocked volcanic rock of the targets, but none has proven reliable. Here, we propose to use cathodoluminescence (imaging and spectrometry), whose intensity is inversely correlated with the degree of shock metamorphism experienced by the investigated lithology, to aid in such a distinction. Specifically, impact melt rocks display low cathodoluminescence intensity, whereas unshocked volcanic rocks from the area typically show high luminescence. This high luminescence decreases with the degree of shock experienced by the individual clasts in the impact breccia, down to almost undetectable when the groundmass is completely molten. This might apply only to El'gygytgyn, because the luminescence in volcanic rocks might be due to devitrification and recrystallization processes of the relatively old (Cretaceous) target rock with respect to the young impactites (3.58 Ma). The alteration that affects most samples from the drill core does not have a significant effect on the cathodoluminescence response. In conclusion, cathodoluminescence imaging and spectra, supported by Raman spectroscopy, potentially provide a useful tool for in situ characterization of siliceous impactites formed in volcanic target.