Organically modified silicates (ORMOSILs) are attractive materials due to their vast applicability and easy synthesis. The doping of these materials with sodium dodecyl sulfate (SDS) is interesting in the search for good protonic conductors. The inclusion of different concentrations of SDS in ORMOSIL membranes is investigated in the present work using Raman and infrared spectroscopy, confocal Raman microscopy and confocal imaging microscopy. The spectroscopic measurements allow us to assign the vibrational modes to the chemical groups of the structures of SDS and ORMOSIL. Furthermore, these measurements show that these materials are composites, as no interactions are observed between the SDS and the ORMOSIL matrix. The confocal Raman and confocal imaging techniques are useful to study qualitatively the SDS insertion on the surface of ORMOSIL. It was observed that the SDS sizes are very nonuniform. Copyright © 2011 John Wiley & Sons, Ltd.