Waste paper as a kind of biomass contains a great quantity of cellulose which is a renewable energy resource. However, complex cellulose supramolecular structure restricts the conversion of waste paper in near-critical water. This study aimed to investigate the change characteristics of cellulose supramolecular structure (hydrogen bond models and crystallinity) during hydrolysis and its effects on 5-HMF yield. Waste paper has been treated in near-critical water at 375 degrees C and 22.5 MPa for a reaction time (160 -240 s) and correlation between 5-HMF yield and the supramolecular structure of cellulose residues has been built up. The 5-HMF yield was increased with the increase of intermolecular hydrogen bonds content in cellulose residues and was increased first and then decreased with the increase of crystallinity of cellulose residues. The rate of decrystallization was out of sync with that of depolymerization, which also influenced 5-HMF yield. Reaction time can be a macro method to adjust the supramolecular structure of cellulose during the conversion of waste paper to obtain more 5-HMF. It showed that 5-HMF yield reached maximum 9.41% +/- 0.47% when the intermolecular hydrogen bonds content of cellulose in residue was 67.77% and the crystallinity of cellulose in residue was 57.14% at 200 s. (C) 2015 Elsevier Ltd. All rights reserved.