Preserving the native β-O-4 bonds in lignin by averting recondensation reactions during biomass fractionation is the key priority for lignin-first biorefinery[1]. Herein, a hemicellulose derived aromatic nucleophile was explored as a capping agent to produce arylated-lignin via selective Cα-arylation thereby suppressing lignin recondensation. This fractionation approach was studied using model compounds, which exhibited near quantitative yields. The fractionation of hemp shives was performed in formic acid at varying time and temperatures. At 100°C, 26.3% of arylated lignin was precipitated leaving behind 40% of residual pulp. The theoretical maximum yield of arylated lignin from hemp shives was calculated to be 29.5%. All the unreacted reagents were recovered and reused for further fractionation of hemp shives. The pulp could be upscaled to nanocellulose (ligno-nanocellulose) and the arylated lignin can be further functionalized to make biobased polymers and biocomposites, thereby contributing to holistic biomass valorization.