Ordered mesoporous carbon (CMK-3) supported nanoscale zero-valent iron (nZVI) composites were synthesized and used for the removal of trichloroethylene (TCE). The nZVI/CMK-3 composites exhibited high TCE removal efficiency in a batch study, which was 2.5 times that of nZVI alone. They also displayed excellent reusability, with 65.2% removal efficiency after three treatments. Dechlorination dominated the process of TCE removal (75.3%–79.4%), whereas adsorption accounted for 20.6%–24.7%. CMK-3 enhanced the dechlorination rate and efficiency of TCE by nZVI, and the enhancement was favored with the increase in CMK-3 content. The Tafel analysis and H2 evolution experiments indicated the mechanisms of CMK-3 action in nZVI/CMK-3 composites for TCE removal. CMK-3 serves as a direct electron transfer, whereas CO was identified as the functional group involved; the other involved the acceleration of redox reaction of atomic hydrogen owing to the superior hydrogen adsorption capacity of CMK-3. The present study provides new perspectives for seeking more efficient nZVI to reinforce the dechlorination process; however, more studies are warranted in the long-term performance of nZVI/CMK-3 in the aquifer condition.