The aim of this PhD thesis is the preparation and study of new materials to be used as electrolytes in Direct Methanol Fuel Cells (DMFC) in order to reduce crossover of methanol. Different materials have been prepared, including polymer dispersed liquid crystals, crosslinked polymers with high protonic conductivity and polymeric liquid crystals. Moreover, a methodology to characterise potential new materials for their application in DMFC has been developed. The absorption properties of water and methanol in the materials have been studied in different conditions and compared with the results obtained for commercial Nafion membranes used in DFMC. The absorption and diffusion properties of water and methanol through the materials have been studied by means of Fourier Transform Infrared Spectroscopy and thermal analysis techniques. The methodology provides important information to analyse the interactions between the different functional groups of the polymers and the solvents commonly used in DMFC. Finally, a device has been designed and set-up to analyse the effect on crossover of methanol of the electro-osmotic drag and the polarisation of the polymeric electrolytes.