The scarcity of fresh water, which is aggravated by rapid economic development and population growth, is a major threat to the modern world. Solar-driven interfacial desalination and steam generation is a promising strategy that localizes heat at the air-water interface through appropriate thermal management and demonstrates efficient photothermal performance. In the current study, Ag, black TiO2, and nitrogen-doped 3D reduced graphene oxide (3D black TiO2/Ag/N@rGO) hierarchical evaporator was fabricated, and its morphology, elemental composition, porosity, broadband solar absorption potential, photothermal performance, and interfacial desalination potential were assessed. The 3D solar evaporator showed efficient solar absorption over the entire broadband UV-visible near-infrared (UV-Vis NIR) region and demonstrated 99% photothermal conversion efficiency and potential freshwater generation of 1.43 kg·m−2 h−1. The specific surface area and porosity analyses demonstrated an ultrahigh specific surface area, high pore volume, and a mesoporous structure, with a predominant pore diameter of 4 nm. The strong photothermal performance can be attributed to the nitrogen doping of the rGO, which boosted the electrocatalytic and photothermal activity of the graphene through the activation of the excess free-flowing π electrons of the sp2 configuration of the graphene; the broadband solar absorption potential of the black TiO2; and the localized surface plasmon resonance effect of the AgNPs, which induced hot electron generation and enhanced photothermal conversion. Hence, the high photothermal conversion efficiency attained can be attributed to the synergistic photothermal performances of the individual components and the high interfacial surface area, abundant heat, and mass transfer microcavities of the 3D hierarchical porous solar absorber, offering multiple reflections of light and enhanced solar absorption. The study highlights the promising potential of the 3D evaporator for real-word interfacial desalination of seawater, helping to solve the water shortage problem sustainably.