Solar steam generation is a highly promising technology for harvesting solar energy, desalination and water purification. We introduce a novel bilayered structure composed of wood and graphene oxide (GO) for highly efficient solar steam generation. The GO layer deposited on the microporous wood provides broad optical absorption and high photothermal conversion resulting in rapid increase in the temperature at the liquid surface. On the other hand, wood serves as a thermal insulator to confine the photothermal heat to the evaporative surface and to facilitate the efficient transport of water from the bulk to the photothermally active space. Owing to the tailored bilayer structure and the optimal thermo-optical properties of the individual components, the wood GO composite structure exhibited a solar thermal efficiency of similar to 83% under simulated solar excitation at a power density of 12 kW/m(2). The novel composite structure demonstrated here is highly scalable and cost-efficient, making it an attractive material for various applications involving large light absorption, photothermal conversion and heat localization.