Reconstructing carbon nanomaterials (e.g., fullerene, carbon nanotubes (CNTs), and graphene) to multidimensional networks with hierarchical structure is a critical step in exploring their applications. Herein, a sacrificial template method by casting strategy is developed to prepare highly flexible and free-standing carbon film consisting of CNTs, graphene, or both. The scalable size, ultralight and binder-free characteristics, as well as the tunable process/property are promising for their large-scale applications, such as utilizing as interlayers in lithium-sulfur battery. The capability of holding polysulfides (i.e., suppressing the sulfur diffusion) for the networks made from CNTs, graphene, or their mixture is pronounced, among which CNTs are the best. The diffusion process of polysulfides can be visualized in a specially designed glass tube battery. X-ray photoelectron spectroscopy analysis of discharged electrodes was performed to characterize the species in electrodes. A detailed analysis of lithium diffusion constant, electrochemical impedance, and elementary distribution of sulfur in electrodes has been performed to further illustrate the differences of different carbon interlayers for Li-S batteries. The proposed simple and enlargeable production of carbon-based networks may facilitate their applications in battery industry even as a flexible cathode directly. The versatile and reconstructive strategy is extendable to prepare other flexible films and/or membranes for wider applications.