Rice straw was mechanically milled using a process consuming 1.9 MJ/kg-biomass, and 10 g/L of unmilled or milled rice straw was used as the carbon source for methane fermentation in a digester containing carbon fiber textile as the supporting material. Milling increased methane production from 226 to 419 mL/L/day at an organic loading rate of 2180 mg-dichromate chemical oxygen demand/L/day, corresponding to 260 mL(CH4/gVS). Storage of the fermentation effluent at room temperature decreased the weight of the milled rice straw residue from 3.81 to 1.00 g/L. The supernatant of the effluent was subjected to nanofiltration. The black concentrates deposited on the nanofiltration membranes contained 53.0-57.9% lignin. Solution nuclear magnetic resonance showed that lignin aromatic components such as p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) were retained primarily, and major lignin interunit structures such as the beta-O-4-H/G unit were absent. This combinational process will aid the complete utilization of rice straw. (C) 2016 Published by Elsevier Ltd.