For the first time, graphene-phosphorene structures were synthesized using the plasma-assisted electrochemical method. The catalytic activity of the composite obtained in the electrolytic plasma mode and its mixtures with few-layer graphene structures toward the hydrogen evolution reaction was studied. A substantial increase in the catalytic activity of the phosphorene structures towards the hydrogen evolution reaction was realized by mixing them with few-layer graphene structures. The catalyst demonstrates excellent activity towards the hydrogen evolution reaction in alkaline media with a low overpotential of 940 mV at a current density of 10 mA·cm−2 and a small Tafel slope of 130 mV dec−1.