Honeycomb-like nanofibrous membranes (NFMs) are promising nanomaterials that can be used in tissue engineering, drug delivery, and water harvesting; however, enhancing the mechanical properties of these nanomaterials has proven extremely challenging. Herein, we report a biomimetic, super-flexible, highly elastic, and tough NFM-based water/fog harvester with a highly-ordered gradient honeycomb-like network structure self-assembled from electrospun spider-silk-like humped nanofibers. The resultant NFM exhibits super flexibility, strengthening (2.9 MPa), high elasticity, and toughening (3.39 MJ m− 3), allowing it to be used as the framework of hygroscopic materials. The resulting hygroscopic NFM displays excellent moisture absorption performance. It can be used as a water/fog harvester with superhigh equilibrium moisture absorption capacity of 4.60 g g− 1 at 95% RH, fast moisture absorption and transport rates, and long-term durability, achieving directional transport and collection of tiny water droplets. This work paves the way for the design and development of multifunctional NFMs with gradient honeycomb-like network structure.