The possibility of modifying the nafion direct alcohol fuel cell proton-exchange membrane by monolayer graphene by hot pressing has been demonstrated. It is shown that this modification can reduce the permeability of the membrane on methanol while maintaining a high proton conductivity membrane, but with the long operation of the membrane without additional protection of the barrier layer formed in this way, it is detached. With a Nafion/graphene/Nafion membrane, the formed graphene layer is sufficiently protected to reduce the methanol crossover and increase the power of the single methanol fuel cell by 2 times.