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Pretreatment with acidified monophasic phenoxyethanol (EPH) efficiently removed 92.6\u2009% lignin and 80\u2009% xylan from poplar at 110\u2009\u00b0C in 60\u2005min, yielding high\u2010value EPH\u2010xyloside, EPH\u2010modified lignin (EPHL), and a solid residue nearly purely composed of carbohydrates. After removing the grafted acetyl groups using 1\u2009% NaOH at 50\u2009\u00b0C, the highest enzymatic digestibility reached 92.3\u2009%. EPHL could be recovered in high yield and purity with an uncondensed structure, while xylose was converted to EPH\u2010xyloside, a potential precursor in biomedical industries. 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