Column studies were conducted to investigate the influence of benzene or toluene on the dechlorination of perchloroethene (PCE) and trichloroethene (TCE) in columns packed with zero-valent iron (ZVI) in order to simulate a permeable reactive barrier (PRB). Enhancive and inhibitive influences of benzene and toluene, respectively, on PCE and TCE reduction were observed within 10–80 pore volumes (PV) that flowed through the columns. However, such influences dissipated when the flow-through volume increased above 80 PV. The presence of benzene increased the mean dechlorination kobs of PCE and TCE by 7% and 6%, respectively; in contrast, the presence of toluene decreased the mean dechlorination kobs of PCE and TCE by 21% and 10%, respectively. We presumed that the more competitive adsorption between benzene and toluene in comparison to PCE and TCE on the ZVI particle surface might have caused the disparate influences. With a lower affinity for ZVI, benzene has no substantial influence on PCE and TCE adsorption on the ZVI particle surface. However, toluene has a higher affinity for ZVI and could compete with PCE and TCE by contacting the ZVI particle surface. Moreover, given benzene's higher polarity, it could also benefit electron transfer from ZVI to PCE and TCE.