This study aimed to produce furfural from the PHL. Results showed best furfural yield of 32.8% and the furfural selectivity of 37.7% in the monophase system (170 °C, 100 min), while they were 60.1% and 69.8%, respectively in the biphase system. The lower furfural selectivity in the monophase system was explained by more side reactions, such as fragmentation, condensation reactions, resinification and others. Model compounds such as: xylose, furfural, syringaldehyde, were used to confirm/identify these side reactions. The addition of dilute sulfuric acid/acetic acid in the system under the same conditions decreased the recovery of furfural. The addition of syringaldehyde into the PHL also led to a decrease in the furfural yield, supporting the conclusion that lignin structures in the PHL may also be involved in the side reactions, thus decreasing the furfural yield.