The alkaline fractionation of rice husk (RH) with NaOH was optimized for the purpose of obtaining a high-yield recovery of glucan and increasing the removal rate for lignin and ash, resulting in a hemicellulose-rich hydrolysate. The determined optimal conditions were a temperature of 150 °C, reaction time of 45 min, and NaOH concentration of 6% (w/v). The glucan content in the fractionated RH (Fr. RH) was 80.1%, which was significantly increased compared to the raw RH (35.6%). High glucan content in the fractionated solid residue is the most essential factor for minimizing enzyme dosages in enzymatic saccharification. The final enzymatic digestibilities (at 96 h) of raw and NaOH-Fr. RH with cellulase loadings of 30 FPU/g cellulose were 10.5% and 81.3%, respectively. Approximately 71.6% of the xmg content (mainly xylose) was concomitantly degraded into the fractionated hydrolysate (Fr. Hydrolysate). When this hydrolysate was acidified with sulfuric acid and subjected to heat treatment, a furfural production yield of about 64.9% was obtained. The results show that two-stage fed-batch fermentation with glucan-rich Fr. RH has the potential to achieve high-ethanol titers of 28.7 g/L.