Interfacial water evaporation, powered by solar energy, holds great promise to extract freshwater from seawater on a global scale. It has the potential to address the world's water scarcity challenges using renewable energy. While the ideal design of evaporator materials is critical to the interfacial vaporization desalination, tailoring the structures and compositions of solar evaporators and figure out the structure/composition-performance relationship of evaporators remains unexplored. Herein, 3D macroporous "brick-concrete" MXene/sodium alginate aerogel (MSA) evaporators were designed and fabricated with constant MXene content and varying polymer loading. The as-made MSAs show sodium alginate-dependent evaporating performance with an optimum evaporation rate of 3.28 kg m−2 h−1 (1 sun). This exceptional rate is attributed to several factors, including enhanced light absorption, optimized pore sizes, reduced enthalpy of evaporation and improved water transport. The water molecule states and hydrogen bonding network in the aerogels can be tuned by their compositions, resulting in the reduced evaporation enthalpy, the monolithic structures with controlled thermal conductivity facilitate the exploitation of environmental energy, leading to the high evaporation rate. Our study not only establishes design principles for achieving superior evaporation performance, but also sheds light on the relationship between structures, compositions, and performance of solar evaporators.