In this study, alkali treatment was used to preferentially separate hemicellulose, and the structural changes of lignin and lignin-carbohydrate complexes (LCC) in the residual bamboo solids were investigated. The chemical composition and structural characteristics of lignin and LCC were analyzed. After alkali treatment, the monosaccharide content in bamboo lignin decreased from 7.62 % to 2.90 % compared to the raw material. The obtained lignin exhibited higher purity and larger molecular weight, with the macromolecular lignin linked by β-O-4′ bonds remaining almost undegraded. After alkali treatment, the linkage bonds in the Björkman LCC were composed of phenyl glycoside (PhGlc), and the bond in LCC-AcOH consisted of benzyl ether (BE). The results showed that the preferential extraction of hemicellulose preserved the biopolymer structure of lignin in bamboo, thereby providing an important basis for the comprehensive separation and utilization of bamboo components.