The synergistic effect of alkaline pretreatment and Fe dosing on anaerobic digestion of maize straw was investigated using mesophilic batch reactors. Three straw treatments were investigated as follows: NaOH (4% and 6%) pretreatment, Fe dosage (50, 200, 1000 and 2000 mg/L), and combined NaOH pretreatment and Fe dosage. Compared to the control, NaOH pretreatment alone increased methane yield by 3.5% (313.3 mL CH4/gVS) and 22.5% (370.9 mL CH4/gVS) and shortened the technical digestion time (TDT) from 48 days to 19 days and 10 days in 4% NaOH and 6% NaOH pretreatment respectively. Moreover, Fe dosing (200-1000 mg/L) alone gave a methane yield higher (9.4%) than that obtained from 4% NaOH and 7.5% less than the methane yield from 6% NaOH pretreatment; however, the TDT was 10 days longer. Combining NaOH pretreatment and Fe dosage (200-1000 mg/L) significantly increased the methane yield even further to 21.8% (368.8 mL CH4/gVS) and 56.2% (472.9 mL CH4/gVS), and shortened TOT from 48 days to 13 days and 7 days in 4% NaOH and 6% NaOH pretreatment respectively. This synergistic effect may be attributed to the fact that the alkaline treatment improved accessibility of the biodegradable fraction of the straw while Fe contributed to increased microbial enzyme activity. (C) 2015 Elsevier Ltd. All rights reserved.