Novel oxygen-releasing bead (ORB) and oxygen-releasing immobilized cell bead (ORICB) were prepared. Their oxygen releasing characteristics and effect on degradation of benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated groundwater were evaluated in a column. ORB prepared by CaO2-encapsulated freezing had much better oxygen-releasing capacity (0.526 mg O2 per ORB) than that by the mixing-freezing method. The encapsulated-ORB did not influence groundwater pH. Two BTEX degraders were utilized to prepare the ORICB. The ORICBs-column rapidly (hydraulic retention time: 0.872 day) degraded BTEX after a 2–5 day acclimation period. The BTEX removal increased as flow distances increased. At BTEX concentration of 120 mg L−1, 67% of benzene and 81–90% of TEX were removed. The SEM shows that micropores existed in the ORBs and BTEX degraders were immobilized. The denaturing gradient gel electrophoresis profiles indicate that BTEX degraders were distributed throughout the column. The BTEX concentration of 120 mg L−1 markedly altered the structure of the indigenous microbial community.