Effective separation of cellulose and hemicellulose from lignocellulosic biomass is an essential step for creating high-value products. In this study, a modified treatment process was proposed for cellulose purification via microwave-assisted formic acid catalytic hydrolysis followed by cold caustic extraction. The sugar content in the extract was determined using UV spectrophotometer and dual-wavelength visible spectrophotometry. Combined microwave-assisted formic acid (M-FA) with cold caustic extraction (CCE) treatments achieved rapid separation and removal of hemicelluloses from waste hardwood pulp fibers. The hemicelluloses content decreased from 28.6% to 2.3%, and the lignin content changed from 27.8% to 6.1%, which resulted in a maximal cellulose content of 91.5% under the optimal M-FA/CCE treatment conditions. In addition, the crystallinity index of pulp fibers increased from 54.3% to 67.1%, and the initial decomposition temperature decreased from 335.4 to 270.2 °C with the decrease of hemicellulose and lignin content. The modified process provided a sustainable and effective method for hemicellulose separation and lignin removal from cellulosic fibers.