Biomass/waste‐based porous carbon (PC) has been treated as the potential anodes for lithium‐ion battery (LIB). Nevertheless, significant challenge appears because it usually exhibits low inheritability of the nanostructure upon activation. In this work, we develop a kind of fiber‐like PCs for LIBs application by choosing waste cotton gloves as the carbon source. The obtained activated carbon fiber (ACF) shows a superior inheritable fiber‐like morphology and thus presents a SBET (Brunauer‐Emmett‐Teller surface area) of 1708 m2 g−1 coupled with a macro/meso/microporous structure. This kind of well‐inherited fiber framework is believed to reduce the electron migration resistance, while the hierarchically macro/meso/microporous structure can reduce the diffusion/transport resistance of the electrolyte and simultaneously increase the utilization of the surface area for Li+ storage. As a result, the obtained ACF exhibits attractive lithium storage performances, including a better reversible capacity of 515 mAh g−1 and high‐rate capability in comparison to most biomass/waste‐based PCs.