Polyoxymethylenedimethylethers CH3-O-(CH2-O)(n)-CH3 with n varying from I to 4 are studied for a possible application as fuels in PEMFC. Cyclic voltarnmetry is performed at Pt, Pt/Ru(50/50), Pt/Ru(80/20) electrodes in acidic medium to evaluate their electroactivity. Electrical performance of the fuels are evaluated in a 5 cm 2 direct fuel cell for different temperatures and pressures with Pt and PL/Ru(50/50) catalysts at the anode and Pt at the cathode. The determination of the reaction products is performed in a 25 cm(2) direct fuel cell under working conditions at constant current for 3 h. Preliminary results are very promising regarding achieved power densities. Results pointed out the important role of hydrolysis of these compounds into methanol and formaldehyde in electroreactivity. It is probable that the cell performances are due to the oxidation of the products coming from hydrolysis rather than to direct oxidation of the polyoxymethylenedimethylethers. Polyoxymethylenedimethylethers appear to be attractive candidates as alternative to methanol, which moreover is a toxic (neurotoxin) molecule. (c) 2007 Elsevier B.V. All rights reserved.