Conversion of organic matter to biohydrogen possesses promising application potential. In this study, low-cost ferrihydrite nanorods were used to enhance hydrogen production by Clostridium pasteurianum. The maximum cumulative hydrogen production and the hydrogen yield were 1.03 mmol and 3.55 mol H-2/mol glucose, respectively, which were 68.9% and 15.6% higher than those of the batch groups without ferrihydrite addition. Moreover, in comparison with magnetite and hematite nanoparticles, ferrihydrite presented the best stimulation for hydrogen evolution. The enhancement mechanisms were explored based on metabolic distribution, gene expression, enzymatic activity, and metabolite determination, such as Fe(II) concentration and pH value. The potential stimulation mechanisms are summarized as follows: ferrihydrite improves glucose conversion efficiency and promotes cell growth; ferrihydrite elevates the transcripts and activity of hydrogenase; and ferrihydrite reduction via its buffer function could ease acidification. This study demonstrates that ferrihydrite addition is an effective and green strategy to enhance fermentative hydrogen production.