As a typical conversion alloyed anode material, Germanium selenide (GeSe2) exhibits isotropic lithiation behavior and high theoretical charge-discharge specific capacity. However, pure GeSe2 anode faces significant volume expansion (∼250 %−360 %) and further exploration is needed in the preparation of flexible electrode materials and structural design. Herein, a simple strategy is designed to load GeSe2/C-2 nanoparticles with porous carbon-coated structure on a flexible cross-networking substrate. The 3D network substrate is composed of highly conductive carbon nanotubes and adhesive cotton cellulose fibers. A two-step method involving coating and cross-linking is designed to achieve the fabrication of self-supporting flexible electrodes. As an anode for LIBs, the one layer GeSe2 discs with ∼0.65 mm thickness manifest capacities of 827.1, 744.4, 676.3, and 472.9 mAh g−1 at 0.1, 0.2, 0.5, and 1 A g−1, respectively. This superior Li+ storage performance can be attributed to the positive collective impact from the integration of nano-scale material, low crystalline properties, and carbon sponge skeleton. Furthermore, the GITT tests indicate that the diffusion coefficient of Li+ in the GeSe2-based electrodes ranged from 10−15 to 10−12 cm2/s, and the thickness of the flexible electrode (including two layers) has a negligible impact on its electrochemical performance.