Applications of cellulose-based materials that require high-purity cellulose as a feedstock are becoming increasingly common. However, reported methods for hemicellulose removal are comparatively complicated. In this study, a Lewis base-enhanced high-temperature liquid water (HTLW) treatment was used to purify cellulose. The variation of carbohydrate content, average degree of polymerization (DP), and the crystalline index of specimens of the purified cellulose were investigated. After primary HTLW treatment, the alpha-cellulose content of specimens increased distinctly; also, the alkali solubility decreased. The DP of the specimens decreased dramatically after HLTW treatment. The incorporation of a Lewis base was beneficial for maintaining DP and for removing hemicellulose selectively. Simultaneously, the results of Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) showed that the chemical and crystal structure of the specimens were unchanged. Based on the experimental results, Lewis base-enhanced HTLW is a promising method to prepare high-purity cellulose.