Optimizing the water bonding network in an evaporator is significant for efficient solar-driven vapor generation (SVG). Herein, we report a facile one-pot method to regulate the hydrated structure and wettability in a hierarchical porous hydrogel. An ovalbumin (OVA)-polyacrylamide hydrogel foam was fabricated in a cake-making fashion. Because of the enrichment of amphiphilic OVA at the interface, the hydrophobic walls of the air pores in the foam provide vaporization sites and help reduce parasitic heat loss, while the hydrophilic skeleton with the secondary pores effectively pumps capillary water. Notably, the proportion of intermediate water in the foam reaches 87.6% with the melting point as low as -10 °C. All these features contribute to an exceptional evaporation rate of 3.4-4.5 kg m -2 h -1 under 1 sun and robust SVG performances at high-humidity, weak sunlight, or cold weathers. The strategy of using amphiphilic molecules to optimize the hydrated structures both at the interface and in bulk promises the reasonable design of SVG materials with superior efficiency and weather adaptability.