Removal of methane, benzene and toluene was evaluated in a lab-scale biocover packed with a soil mixture of forest soil and earthworm cast (75:25 weight ratio). The bacterial community in the biocover was characterized using quantitative real-time PCR and terminal restriction fragment length polymorphism. Methane was removed at the upper layer of the biocover (-0.1 ~ -0.4 m), where the oxygen concentration was remarkably lower. The average removal efficiencies for methane and benzene/toluene were 90% and 99%, respectively. The pmoA gene copy numbers, responsible for methane oxidation, in the upper layer were higher than those in the lower layer. While type I methanotrohs dominated the lower layer, type II methanotrophs, such as Methylocystis and Methylosinus, were noted to be predominant in the upper layer. Benzene and toluene were removed from the lower layer (-0.6 ~ -0.9 m) as well as the upper layer. Moreover, the tmoA gene copy number, responsible for benzene/toluene oxidation, seen in the upper layer was not significantly different from those seen in the lower layer. These results suggest that a biocover packed with a soil and earthworm cast mixture is a promising method which could be utilized for the control of methane and volatile organic compounds such as benzene and toluene.