Ingenious microstructure construction and appropriate composition selection are effective strategies for achieving enhanced performance of photothermal materials. Herein, a broccoli-like hierarchical nickel black@graphene (Ni@Gr) membrane for solar-driven desalination was prepared by a one-step electrochemical method, which was carried out simultaneously with the electrochemical exfoliation of graphene and the co-deposition of Ni@Gr material. The bionic hierarchical structure and the chemical composition of the Ni@Gr membrane increased the sunlight absorption (90.36%) by the light-trapping effect and the introduction of graphene. The Ni@Gr membrane achieved high evaporation rates of 2.05 and 1.16 kg m