Solar‐powered interfacial heating has emerged as a sustainable technology for hybrid applications with minimal carbon footprints. Aerogels, hydrogels, and sponges/foams are the main building blocks for state‐of‐the‐art photothermal materials. However, these conventional three‐dimensional (3D) structures and related fabrication technologies intrinsically fail to maximize important performance‐enhancing strategies and this technology still faces several performance roadblocks. Herein, monolithic, self‐standing, and durable aerogel matrices are developed based on composite photothermal inks and ink‐extrusion 3D printing, delivering all‐in‐one interfacial steam generators (SGs). Rapid prototyping of multiscale hierarchical structures synergistically reduce the energy demand for evaporation, expand actual evaporation areas, generate massive environmental energy input, and improve mass flows. Under 1 sun, high water evaporation rates of 3.74 kg m−2 h−1 in calm air and 25.3 kg m−2 h−1 at a gentle breeze of 2 m s−1 are achieved, ranking among the best‐performing solar‐powered interfacial SGs. 3D‐printed microchannels and hydrophobic modification deliver an icephobic surface of the aerogels, leading to self‐propelled and rapid removal of ice droplets. This work shines light on rational fabrication of hierarchical photothermal materials, not merely breaking through the constraints of solar‐powered interfacial evaporation and clean water production, but also discovering new functions for photothermal interfacial deicing.

Environmental humidity and thermal control are of primary importance for fighting global warming, growing energy consumption, and greenhouse gas emissions. Sorption-based atmospheric water harvesting is an emerging technology with great potential in clean water production and passive cooling applications. However, sorption-based humidity management and their hybrid applications are limited due to the lack of energywise designs of hygroscopic materials and devices. Herein, all polymeric 3D foams are developed and evaluated as hygroscopic and photothermal materials. The gas-foaming method generates closed-cell structures with interconnected hydrophilic networks and wrinkled surfaces, expanding hygroscopic, photothermal, and evaporating areas of the 3D foams. These unique advantages lead to efficient water vapor sorption in a wide broad relative humidity (RH) range of 50−90% and efficient water release in a wide solar intensity (0.4−1 sun) and temperature range (27−80 °C). The reversible moisture sorption/release in 50 adsorption/desorption cycles highlights the excellent durability of the 3D foams compared to conventional inorganic desiccants. The 3D foams disclose passive and efficient apparent temperature regulation in warm and humid environments. Moreover, the use of the 3D foams as loose fill for fruit preservation and packaging is demonstrated for the first time by taking the merit of the 3D foams' moisture-absorbing, quick-drying, cushioning, and thermal-insulating properties. This work presents an integrated design of polymeric desiccants and scaffolds, not merely delivering stable water adsorption/desorption but also discovering innovative hybrid applications in humidity management and protective packaging.