With the development of society, there is an increasing demand for high-quality drinking water. Groundwater, as an important drinking water source, is facing a serious issue of pollution from oxidized contaminants. In recent years, the gaseous alkane-based membrane biofilm reactor (MBfR) has demonstrated exceptional efficacy and advantages in treating oxidized contaminants in groundwater. This review elucidates the underlying principles and technical characteristics of the gaseous alkane-based MBfR in the bioreduction of oxidized contaminants. Additionally, the feasibility and effectiveness of this approach in degrading various types of oxidized contaminants, including perchlorate and nitrate, are discussed. Furthermore, the related functional enzymes and core microorganisms, such as alkane-oxidizing bacteria and contaminant-reducing bacteria, are elucidated in the gaseous alkane-driven oxidized contaminants reduction process, and the microbiological mechanisms involved in this process are illuminated. Finally, we propose the challenges encountered by this technique in practical application, and shed light on corresponding solutions. This review not only provides novel insights for green and low-carbon management of oxidized pollutants in groundwater, but also bears significant theoretical implications for the utilization of natural gas and development of new technologies for groundwater remediation.