Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely distributed solar energy and alleviate the world's freshwater scarcity. Herein, an amphiphilic photothermal membrane is prepared through the self-assembly of hydrophilic heteropoly blue (HPB, H3 PM012 O40) and hydrophobic surfactant (dioctadecyl dimethyl ammonium bromide, DODA). Benefiting from the synergistic effects of alternating functional hydrophilic HPB and hydrophobic DODA layers, the flexible membrane based on two-dimensional DODA-HPB self-assemblies (DODA-HPB/Nylon66) exhibits superior photothermal conversion properties, showing promising prospects in applications of solar desalination and wastewater treatment.