Gallium oxide (Ga2O3) is one of the most promising anode materials for lithium‐ion batteries due to its high theoretical specific capacity and ability to maintain self‐healing behavior during the reaction process. However, the susceptibility to volume expansion during the alloying reaction, which affects cycling performance, and the unclear lithium storage mechanism limit the application of Ga2O3. For this purpose, α‐Ga2O3@ chitosan‐derived carbon nanocomposites (α‐Ga2O3@CS NPs) were synthesized by introducing biomass materials. Due to the capacity contribution of Ga2O3 and the inhibition of biomass carbon on volume expansion, the composites exhibit excellent electrochemical performance. A high reversible capacity was shown in the long‐cycle test, with a discharge capacity of 505.1mAh g‐1 after 130 cycles at 0.2 A g‐1, with no significant decrease from the initial capacity. During the periodic rate performance test of 0.1 to 5A g‐1, the reversible discharge capacity of the electrode material was maintained at 482.2 mAh g‐1 when the current was restored to 0.1 A g‐1. In addition, the lithium storage process of the electrode was investigated by in‐situ X‐ray diffraction (in‐situ XRD), which, together with the low‐cost synthesis process, promoted the practical application prospect of Ga2O3.This article is protected by copyright. All rights reserved.