Although a solar-thermal conversion technique shows great potential for seawater desalination, there remains a grand challenge in exploring low-cost and high-efficiency photothermal materials. We report here a molten salt assisted galvanic replacement method for preparing a hollow black TiAlOx composite, which features a high solar absorptivity with up to 90.2% and has a high efficiency of 71.1% in a high salinity solution containing 15.3 wt% NaCl (∼5 times more concentrated than seawater). We exemplify the practical application of such hollow black TiAlOx composites as photothermal composites by setting up the automatic and manual tracking of solar desalination devices with a photic area of ∼1.0 m2, which can produce purified water with a rate of above 4.0 L m-2 day-1 in high-salinity water under natural light irradiation, and maintains good stability upon 5 days of continuous running. The advantages of the as-developed hollow black TiAlOx composites, including scalability, low cost, and high photothermal conversion efficiency, may open up a promising avenue practical application in seawater desalination.