Herbicide residue and greenhouse gas (GHG) emission are two main problems in the paddy rice field, which have barely been considered simultaneously. Herein, a bensulfuron-methyl (BSM)-degrading bacterium named Acinetobacter YH0317 was successfully immobilized on two kinds of biochars and subsequently applied in the paddy soil. The BSM removal rate of Acinetobacter YH0317 immobilized boron-doping biochar (BBC) was 80.42% after 30 d, which was significantly higher than that of BBC (39.05%) and Acinetobacter YH0317 (49.10%) applied alone. BBC acting as an immobilized carrier could enable Acinetobacter YH0317 to work in harsh and complex environment and thus improve the BSM removal efficiency. The addition of Acinetobacter YH0317 immobilized BBC (TP5) significantly improved the soil physicochemical properties (pH, SOC, and NH4+-N) and increased the diversity of soil microbial community compared to control group (CG). Meanwhile, Acinetobacter YH0317 immobilized BBC reduced the CO2-equivalent emission by 41.0%. Metagenomic sequencing results revealed that the decreasing CO2 emission in TP5 was correlated with carbon fixation gene (fhs), indicating that fhs gene may play an important role in reducing CO2 emission. The work presents a practical and supportive technique for the simultaneous achievement on the soil purification and GHG emission reduction in paddy soil.