Taken common agricultural residues as substrate, dark fermentation bio-hydrogen yield capacity from asynchronous saccharification and fermentation (ASF) and simultaneous saccharification and fermentation (SSF) was investigated. The highest hydrogen yield of 472.75 mL was achieved with corncob using ASF. Hydrogen yield from corn straw, rice straw, corncob and sorghum stalk by SSF were 20.54%, 10.31%, 13.99% and 5.92% higher than ASF, respectively. The experimental data fitted well to the modified Gompertz model. SSF offered a distinct advantage over ASF with respect to reducing overall process time (60 h of SSF, 108 h of ASF). Meanwhile, SSF performed better than SSF with respect to shortening the lag-stage. The major metabolites of anaerobic fermentation hydrogen production by ASF and SSF were butyric acid and acetic acid.