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Arundo donax L. (giant cane) is a suitable feedstock for sugar production because of its high biomass yield and low agronomic input requirement. Eight A. donax clones were studied at full field scale for sugars production. 1‐ethyl‐3‐methylimidazolium acetate ‐ [C2C1im][OAc] ‐ and enzymatic treatments were used to obtain the sugars. Highest glucose yields were obtained for pretreatment performed at 160 °C for 3 hours, with glucan conversion yields from 40.8 % to 76.2 % for most productive A. donax clones (AD10 and AD 20). Differences in cell wall structure measured by micropore surface area (pores of 0.3 ‐ 1.5 nm) explained both ionic liquids and enzymatic performances of clones. Structural differences were due to the guaiacyl (G) and syringyl (S) units that determined different lignin cross‐linking affecting cell wall microporosity and so enzyme accessibility. Total glucose and xylose yields (11 Mg Ha−1 and 4.84 Mg Ha−1, clone AD20), were impressive and about 3.5 to 4.5 times more than those obtainable from switchgrass and corn stover.

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A highly productive Arundo donax L. clone (Clone AD-20) was produced at full field to give 54.6 Mg total solids biomass Ha–1. Biomass was chemically and enzymatically pretreated, recovering 13.9 Mg Ha–1 of glucose and 3.6 Mg Ha–1 of xylose, i.e., 3.5–4.5 more than yield typically obtained from corn stover or switchgrass. The subsequent fermentation of the liberated sugars to organic acids (OA) by dark fermentation generated yields of 3850 Nm3 Ha–1 of biohydrogen and 14.2 Mg Ha–1 of OAs. OAs were then used as a feed to produce polyhydroxyalkanoates (PHA), with 3-hydroxybutyrate the major monomer present (PHB > 95% PHA), from a biological process using mixed microbial culture producing 5.04 Mg Ha–1 of PHA. An initial economic analysis indicated that this multistage biorefinery approach would result in a net revenue of 10,415 € Ha–1, which is approximately 9-fold greater than that obtained by a traditional biorefinery producing bioethanol.