The use of biomass for the production of electrical energy is a promising technological solution for those countries where there are problems with the disposal of agricultural waste and/or the production of low-cost energy. The gasification and/or pyrolysis of the biomass produces a gas rich in hydrogen that can be used in a fuel cell system to produce electrical energy with reduced environmental impact and significant energy recovery. In this work, a study of the pyrolysis of Brazilian sugarcane bagasse was carried out. The experimental process consisted of the pyrolysis of the biomass material in a batch pyrolysis reactor. In some runs the biomass was dry, while in others it was pre-treated by the addition of water. It was noted that the water added to the biomass before the pyrolysis process resulted in a decrease in the quantity of steam added to the fuel cell feeding gas, necessary to avoid carbon deposition, and in an increase in cell power, but, at the same time, caused a decrease in the quantity of syngas produced. Then, the composition of the gas obtained from the experimental pyrolysis of the sugarcane was inserted in a simulation tool of a molten carbonate fuel cell system in order to estimate the feasibility of the entire process in terms of operating conditions and electrical performance. The present study indicates that the syngas obtained from the sugarcane biomass (about 40%) can be converted into electricity using a fuel cell system with a high efficiency.