BACKGROUND: Rice hull, an abundant residue but a big issue for the rice processing industry, has the potential to serve as a feedstock for production of ethanol because of its lignocellulosic composition. Simultaneous wet ball milling and mild acid hydrolysis of rice hull was studied in this work. RESULTS: Ball milling with 150 small stainless steel beads and rotation speed of 600 rpm in citrate solvent of pH 4 was the optimal condition for hydrolysis, and the yield of sugar increased with increased milling time. Corresponding structure transformations before and after milling analyzed by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and transmission fourier transform infrared spectroscopy (FT-IR) clearly indicate that this hydrolysis could be attributed to the crystalline and chemical structure changes of cellulose in rice hull during ball milling in mild acid solvent. CONCLUSION: This combined treatment of ball milling and citrate solvent greatly changed the crystalline and chemical structure and continuously generated sites accessible to citrate solvent, thus enabling hydrolysis of the rice hull. (C) 2009 Society of Chemical Industry