Layered double hydroxideswithMe-based oxyanions (Me_Mo, V) in the interlayer gallerywere prepared by ion exchange and used as efficient catalysts for the mild oxidation of organic sulfideswith H2O2. Raman spectroscopy was used as the main and very efficient technique for the advanced characterization of these materials during their preparation and catalytic use. First, it served for monitoring the progression of the ion exchange during the preparation of the catalysts, and then the Raman spectroscopy provided precise information regarding the type of the oxyanions located in the catalyst structure, before and after the oxidation reaction.