Desalination by solar steam generation (SSG) has emerged as one of the most efficient approaches to address the issue of global water shortage. In this work, novel graphene oxide (GO)-based solar steam generators (GO-SSGs) with aligned channels were prepared by directional freezing and simple carbonization of a hydrogel composed of GO and poly(vinyl alcohol) (PVA). Benefitting from their excellent light absorption (light absorption efficiency exceeds 94%), better thermal insulation (thermal conductivity, 0.259 W/(m K)), and suitable porous structure, which facilitates rapid water transportation, the GO-SSGs show superior SSG performance with a high solar energy conversion efficiency of up to 92% achieved under an irradiation of 1.0 kW/m2. Interestingly, uniquely aligned channels endow them with good salt-rejection performance; the solar energy conversion efficiency of GO-SSGs in 20 wt % NaCl, KCl, and MgCl2 brine can reach more than 85%. To improve their antifouling performance, a chemically hydrophilic and oleophobic modification was conducted, making it possible to run SSG even in oily wastewater; for instance, a solar energy conversion efficiency of 84% was obtained in an aqueous solution containing 10 wt % n-hexadecane. Compared with the existing photothermal materials, these materials show advantages of simple manufacture, high SSG efficiency, superior salt tolerance, and antifouling performance, which make them promising candidates as a kind of new high-performance photothermal materials for desalination even in oily wastewater, thus further expanding the scope of their practical SSG application.