We showed that the dechlorination of carbon tetrachloride (CT) can be significantly enhanced at nearneutral pH by modified Fenton reaction in the presence of Fe(II) chelated by cross-linked chitosan (CS) with glutaraldehyde (GLA). CT dechlorination was verified by monitoring the release of chloride and detection of intermediates such as trichloromethane and dichloromethane in the modified Fenton system with Fe(II) chelated by cross-linked CS with GLA (Fe(II)-CS/GLA). Measured chlorine mass balance of each sample was greater than 91% of total chlorine mass corresponding to initial CT concentration throughout the reaction. Addition of hydroxyl radical scavenger (2-propanol) enhanced the CT degradation in 5 h at near-neutral pH (removal efficiency from 57.2% to 92.4%), while the addition significantly inhibited trichloroethylene (TCE) degradation at the same condition (74.7% to 19.9%). This implies that, in contrast to the dechlorination of TCE, that of CT did not follow an oxidative dechlorination pathway but a reductive dechlorination pathway in the modified Fenton system with Fe(II)-CS/GLA. Dechlorination kinetics of CT in the modified Fenton system was affected by the concentrations of H2O2, Fe(II), and CT. The formation of surface Fe(II)-CS/GLA complex and its valence change from Fe(II) to Fe(III) observed during the modified Fenton reaction gave a clue to identify the proposed reaction mechanism properly.