This work aims to investigate whether and how TCC affects hydrogen production using both experimental and model approaches. Experimental results showed that the exposure of TCC not only enhanced the hydrogen production yield but also promoted the hydrogen yield potential and hydrogen production rate. The maximum hydrogen production yield and hydrogen production rate increased from 10.1 ± 0.2 to 14.2 ± 0.2 mL/g VSS and 0.09 to 0.13 mL/g VSS·h, respectively, when TCC level increased from 0 to 1403 ± 150 mg/kg TSS. Mechanism exploration showed that the presence of TCC significantly promoted the release of substances and observably facilitated the acidification process but seriously inhibited the methonogenesis and homoacetogenesis processes. Further investigations with enzyme analysis revealed that TCC importantly increased the activities of acetate kinase and [FeFe] hydrogenase but seriously inhibited the activities of carbon monoxide dehydrogenase and Coenzyme F420.