Bioethanol was considered as raw material for hydrogen production by steam reforming, coupled with a proton exchange membrane fuel cell for heat and power cogeneration (5 kWelectrical + 5 kWthermal). The water/ethanol feeding ratio and the ethanol purity were considered for process optimisation. An increase of the water/ethanol ratio improved H2 yield at the expenses of higher heat input to the reformer and lower electrical output. However, the presence of a high enthalpy exhaust stream increased the available thermal output, with a consequent increase of the thermal and overall efficiency of the plant. Finally, the bioethanol purification step, which is energy- and cost-intensive, has been taken into account, searching for an optimisation of the bioethanol purification strategy for the overall process intensification.