Solar vapor generation is a facile and an efficient way for solar energy harvesting, which is applied to address the issue of fresh water extraction from sewage or brine. Several solar vapor generation devices have been developed in the past few years, but the low evaporation rate still remains as a challenge. In this work, a novel double-layer solar vapor generation device, named as Ag-PSS-AG/AG device, is reported. This device is based on the hierarchical composition of silver nanoparticles (Ag NPs) and poly (sodiump-styrenesulfonate) (PSS) decorated agarose gel (AG). The device reveals a synergetic effect of the two layers with high light-harvesting and watertransfer performance, respectively, leading to an ultrahigh vapor generation rate of 2.10 kg m −2 h −1 with a solar thermal efficiency of 92.8% under 1 sun illumination. This high evaporation rate is mainly owing to the powerful light-thermal conversion of Ag NPs as well as the outstanding water transfer capability of agarose hydrogel. Consequently, this device can be directly used for the purification of sewage and muddy water. It is also promising for applications in separation, humidity management, and others.NPs embedded in AG skeleton ensures the adequate transfer and full utilization of the converted heat energy. Therefore, the Ag-PSS-AG/AG device exhibits an ultrahigh vapor generation rate of 2.10 kg m −2 h −1 with a solar thermal efficiency of 92.8% under 1 sun illumination.