Abstract Lignin solubilization and in situ hydrogenolysis are crucial for reductive catalytic fractionation (RCF) of lignocellulose to aromatic monomers. In this study, we reported a typical hydrogen bond acceptor of choline chloride (ChCl) to tailor the hydrogen‐donating environment of the Ru/C‐catalyzed hydrogen‐transfer RCF of lignocellulose. The ChCl‐tailored hydrogen‐transfer RCF of lignocellulose was conducted under mild temperature and low‐pressure (<1 bar) conditions, which was applicable to other lignocellulosic biomass sources. We obtained an approximate theoretical yield of propylphenol monomer of 59.2 wt and selectivity of 97.3 using an optimal content of ChCl (10 wt ) in ethylene glycol at 190 °C for 8 h. When the content of ChCl in ethylene glycol was increased to 110 wt , the selectivity of propylphenol switched toward propylenephenol (yield of 36.2 wt and selectivity of 87.6 ). The findings in this work provide valuable information for transforming lignin from lignocellulose into value‐added products.
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