Solar steam generation based on photothermal materials has emerged as a green and efficient technology for a broad variety of applications, such as solar energy harvesting, desalination, power generation, wastewater treatment, and so on. Herein, the fabrication of a kind of a novel photothermal material that is prepared by simple coating of reduced graphene oxide (rGO) onto commercial hollow polyester fibers (HPFs) for efficient solar steam generation is reported. The as‐resulted rGO‐wrapped HPFs possess a porous structure, low thermal conductivity (0.042 W m−1 k−1), and broad light absorption (85%), which satisfies the criterion for construction of ideal photothermal materials. As expected, a high solar‐thermal efficiency of ≈81% is obtained at 1 kW m−2 irradiation, showing great potential for practical applications based on high solar energy conversion efficiency and a simple and, in particular, scalable manufacturing process.