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In this work, four different media including aqueous water, acetic acid (AA), HCl, and H2SO4 were used to hydrolyze holocelluloses. The decomposition of holocellulose and pseudo‐lignin formation are discussed. It was found that AA and water are almost comparable in catalyzing holocellulose (HC) decomposition but the former can promote sugar decomposition and therefore pseudo‐lignin formation. In contrast, HCl and H2SO4 are more efficient in HC decomposition and furfural formation; specifically, HCl is extremely potent for HC decomposition and furfural formation but inert for pseudo‐lignin formation. The results confirmed that both hydrogen ions and anions would affect the carbohydrate decomposition; in this case, further study revealed that only concentrated Cl− in the water system can promote the furfural formation but Cl− with relative low concentration will inhibit pseudo‐lignin formation. It is proved that, Cl− can stabilize the intermediates that facilitate the pseudo lignin formation. © 2021 Society of Industrial Chemistry and John Wiley & Sons Ltd.