The reductive dechlorination and biodegradation of 2,2(')4,5,5(')-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2(')4,5,5(')-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2('),4,5,5(')-pentachlorobiphenyl. In laboratory batch experiments, 2,2(')4,5,5(')-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2('),4-trichlorobiphenyl (PCB#17), a reduction product from 2,2(')4,5,5(')-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.