To accelerate the degradation of substrate, 50% liquid digestate recirculation (LDR) was used in the anaerobic digestion (AD) of corn straw. The effects of recirculation on the enzyme activities and biogas production were investigated by comparing with control reactor (ReactorCK). During the AD process, the fermentation system with 50% LDR was more stable. The average biogas and methane production in ReactorLDR were 7,891 mL·d−1 and 347 mL CH4·g−1 VSadded·d−1 respectively. The total volatile fatty acids (TVFAs) concentration in the two reactors both increased at first and then decreased with time. The LDR made the VFAs accumulation significant, especially propionic acid accumulation in 4 ∼ 16 days. The maximum peak value of cellulase, xylanase, dehydrogenase and coenzyme F420 activities in ReactorLDR were 0.51 mg·g−1·h−1, 0.29 mg·g−1·h−1, 4.88 mL·g−1·h−1 and 6.69 μmol·L−1, respectively, which were higher than that in ReactorCK. With or without recirculation, the concentration of TVFAs was positively correlated with cellulase, xylanase and dehydrogenase activities, while was negatively correlated with coenzyme F420 activity. Besides, a very significant correlation existed between hydrolase and dehydrogenase activities and daily biogas production in ReactorCK. And the peaks of cellulase, xylanase and dehydrogenase activities appeared ahead of the peak of daily biogas production with the LDR.