Increasing consumption produces a large amount of cotton textile waste, the conversion of which into porous metals used for energy purposes is of practical value. In this paper, a porous, Ni-based, hollow microtubular weave (Ni-HTW) is obtained from cotton weave by high-temperature carbonization and hydrothermal synthesis with high-temperature reduction. The Ni-based, hollow microtubules in this weave have a diameter of 5–10 μm and a wall thickness of about 1 μm, and every 15 microtubules form a loose bundle with a diameter of 150–200 μm. For improved performance, Ni(OH)2 nanosheets are further electrodeposited on the fibers’ surface of the Ni-HTW to form a nano-Ni(OH)2/Ni-HTW composite electrode with a core–shell heterostructure where Ni is the core and Ni(OH)2 the shell. The combination of hollow microtubule weave morphology and nanosheet structure results in a large specific surface area and abundant active sites, and the composite electrode shows excellent electrocatalytic performance and long-term stability for methanol oxidation (MOR) and urea oxidation (UOR). The current densities can reach 303.1 mA/cm2 and 342.5 mA/cm2 at 0.8 V, and 92.29% (MOR) and 84.41% (UOR) of the pre-cycle current densities can be maintained after 2000 consecutive cycles.