AbstractOne of the most promising technologies for lignocellulosic biomass utilization employs ionic liquids for the conversion of isolated components into fuels, pharmaceuticals, chemicals, and composites after fractionation of lignocellulose. However, the time required for dissolution of the whole cell wall has been excessive. To explore a possible dissolution and fractionation pathway of lignocelluloses, the dissolution of holocellulose isolated from bagasse was investigated in 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) assisted with ball-milling pretreatment and ultrasound irradiation. Ball milling pretreatment, ultrasonic irradiation assistance, and their combination were found to effectively improve the holocellulose dissolution in [C4mim]Cl. The effects of ultrasound power and irradiation duration on the dissolution time of ball-milled holocelluloses in [C4mim]Cl were studied. The regenerated holocelluloses were characterized with FT-IR, X-Ray, and CP/MAS 13C-NMR. It was found that there were no obvious changes of chemical structure after dissolution and regeneration of the holocellulose. The crystalline structure of cellulose was converted from cellulose I in native holocellulose to cellulose II in the regenerated holocellulose. The crystallinity decreased after the process of dissolution and regeneration assisted by ball-milling pretreatment and ultrasound irradiation.