Intelligent materials with switchable wettability in response to external stimuli are highly desirable for sustainable water harvest from a humid atmosphere. Herein we present the design of a photothermal-responsive material for intelligent moisture capture and release based on marrying thermal-responsive poly(N-isopropylacrylamide) (PNIPAM) to reduced graphene oxide (RGO) with excellent photothermal property. The asdesigned RGO/PNIPAM material could make itself as a heat source through efficiently converting sunlight into heat, driving the wettability change of thermal-responsive PNIPAM from hydrophilic to hydrophobic. Consequently, the RGO/PNIPAM achieves moisture capture with its hydrophilic PNIPAM chains below the low critical solution temperature (LCST) (<32 °C) and complete water release under sunlight illumination through switching the hydrophilicity into hydrophobicity of the PNIPAM. This intelligent photothermal-responsive behavior of RGO/PNIPAM matches nicely with the nature of typical day-and-night change of dry coastal areas, lighting up the practical prospect of RGO/PNIPAM for water harvest from a humid atmosphere. Moreover, the switchable wettability of RGO/PNIPAM is reversible, which endows it with good recyclability in moisture capture and release (e.g., >10 cycles). This study is interesting because it provides a paradigm in the design of intelligent materials for moisture harvest, which may shed light on the design and application of other high-performance stimuli-responsive materials.