Ring-opening graft polymerization (ROGP) of L-Lactide (L-LA) is a practical method of altering the physical and chemical properties of lignocellulose. Previous studies have mainly investigated cellulose and tin-based catalysts, particularly of tin(II) 2-ethylhexanoate (Sn(oct)2), at high temperatures and reported low graft efficiencies. In the present study, ROGP of L-LA was successfully achieved on xylan-type hemicelluloses in ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl) using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an effective organic catalyst. Mild reaction condition (50 °C) was used to limit transesterification, and thus enhance the graft efficiency. The hydroxyl groups on xylan acted as initiators in the polymerization, and DBU, enhanced the nucleophilicity of the initiator and the propagating chain. Xylan-graft-poly(L-Lactide) (xylan-g-PLA) copolymer with a degree of substitution (DS) of 0.58 and a degree of polymerization (DP) of 5.51 was obtained. In addition, the structures of the xylan-g-PLA copolymers were characterized by GPC, FT-IR and NMR, confirming the success of the ROGP reaction. Thermal analysis revealed that the copolymers exhibited a single glass-transition temperature (T g), which decreased with increasing molar substitution (MS). Thus, modification resulted in the graft copolymers with thermoplastic behavior and tunable T g.