Energy crops are not easily converted by microorganisms because of their recalcitrance. This necessitates a pretreatment to improve their biodigestibility. The effects of different pretreatments, as well as their combination on the enzymatic digestibility of Arundo donax L. were systematically investigated to evaluate its potential for bioconversion. Dilute alkaline pretreatment (ALP) using 1.2% NaOH at 120 °C for 30 min resulted in the highest reducing sugar yield in the enzymatic hydrolysis process because of its strong delignification and morphological modification, while ferric chloride pretreatment (FP) was effective in removing hemicellulose and recovering soluble sugars in the pretreatment stage. Furthermore, an efficient two-step ferric chloride-alkaline pretreatment (FALP) was successfully developed. In the first FP step, easily degradable cellulosic components, especially hemicellulose, were dissolved and then effectively recovered as soluble sugars. Subsequently, the FP sample was further treated in the second ALP step to remove lignin to enhance the enzymatic hydrolysis of the hardly degradable cellulose. As a result, the integrated two-step process obtained the highest total sugar yield of 420.4 mg/g raw stalk in the whole pretreatment and enzymatic hydrolysis process; hence, the process is a valuable candidate for biofuel production.