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Background  Peroxyacetic acid involved chemical pretreatment is effective in lignocellulose deconstruction and oxidation. However, these peroxyacetic acid are usually artificially added. Our previous work has shown that the newly developed PHP pretreatment (phosphoric acid plus hydrogen peroxide) is promising in lignocellulose biomass fractionation through an aggressive oxidation process, while the information about the synergistic effect between H 3 PO 4  and H 2 O 2  is quite lack, especially whether some strong oxidant intermediates is existed. In this work, we reported the PHP pretreatment system could self-generate peroxyacetic acid oxidant, which mediated the overall lignocellulose deconstruction, and hemicellulose/lignin degradation.    Results  The PHP pretreatment profile on wheat straw and corn stalk were investigated. The pathways/mechanisms of peroxyacetic acid mediated-PHP pretreatment were elucidated through tracing the structural changes of each component. Results showed that hemicellulose was almost completely solubilized and removed, corresponding to about 87.0% cellulose recovery with high digestibility. Rather high degrees of delignification of 83.5% and 90.0% were achieved for wheat straw and corn stalk, respectively, with the aid of peroxyacetic acid oxidation. A clearly positive correlation was found between the concentration of peroxyacetic acid and the extent of lignocellulose deconstruction. Peroxyacetic acid was mainly self-generated through H 2 O 2  oxidation of acetic acid that was produced from hemicellulose deacetylation and lignin degradation. The self-generated peroxyacetic acid then further contributed to lignocellulose deconstruction and delignification.    Conclusions  The synergistic effect of H 3 PO 4  and H 2 O 2  in the PHP solvent system could efficiently deconstruct wheat straw and corn stalk lignocellulose through an oxidation-mediated process. The main function of H 3 PO 4  was to deconstruct biomass recalcitrance and degrade hemicellulose through acid hydrolysis, while the function of H 2 O 2  was to facilitate the formation of peroxyacetic acid. Peroxyacetic acid with stronger oxidation ability was generated through the reaction between H 2 O 2  and acetic acid, which was released from xylan and lignin oxidation/degradation. This work elucidated the generation and function of peroxyacetic acid in the PHP pretreatment system, and also provide useful information to tailor peroxide-involved pretreatment routes, especially at acidic conditions.    Graphical abstractSupplementary Information  The online version contains supplementary material available at 10.1186/s13068-021-02075-w.

Self-generated peroxyacetic acid in phosphoric acid plus hydrogen peroxide pretreatment mediated lignocellulose deconstruction and delignification