This study explores optimizing hydrogen production from corn stover by investigating the effects of Composite Electric Field Pretreatment (CEP) on enzymatic hydrolysates. Dark fermentation challenges like scum formation and low mass transfer efficiency are addressed. Enzymatic hydrolysate fermentation improves biohydrogen production efficiency by extracting fermentable sugars. Electric field pretreatment, high and low, efficiently reduces biomass recalcitrance and enhances cellulase hydrolysis. The study aims to assess CEP impact on dark fermentation, optimize pretreatment conditions, and elucidate enhancement mechanisms. Results show a 55.3% increase in hydrogen production with CEP, predominantly during acid fermentation. VFAs accumulated during the subsequent alkaline phase, facilitating pH self-regulation. This research presents promising avenues for scaling up hydrogen production and optimizing biofuel efficiency.