Biomass-derived sugars are platform molecules that can be converted into a variety of final products. Non-food, lignocellulosic feedstocks, such as agroforest residues and low inputs, high yield crops, are attractive bioresources for the production of second-generation sugars. Biorefining schemes based on the use of versatile technologies that operate at mild conditions contribute to the sustainability of the bio-based products. The present work describes the conversion of giant reed (Arundo donax), a non-food crop, to ethanol and furfural (FA). A sulphuric-acid-catalyzed steam explosion was used for the biomass pretreatment and fractionation. A hybrid process was optimized for the hydrolysis and fermentation (HSSF) of C6 sugars at high gravity conditions consisting of a biomass pre-liquefaction followed by simultaneous saccharification and fermentation with a step-wise temperature program and multiple inoculations. Hemicellulose derived xylose was dehydrated to furfural on the solid acid catalyst in biphasic media irradiated by microwave energy. The results indicate that the optimized HSSF process produced ethanol titers in the range 43–51 g/L depending on the enzymatic dosage, about 13–21 g/L higher than unoptimized conditions. An optimal liquefaction time before saccharification and fermentation tests (SSF) was 10 h by using 34 filter paper unit (FPU)/g glucan of Cellic® CTec3. C5 streams yielded 33.5% FA of the theoretical value after 10 min of microwave heating at 157 °C and a catalyst concentration of 14 meq per g of xylose.