The detrimental impacts of oily wastewater on the environment and living organisms necessitate effective wastewater treatment methods. MXenes, with their exceptional properties, have garnered significant attention in various fields since their discovery. This review offers a critical summary of the MXene materials to be successfully employed for the efficient separation of various oily emulsions. The unique characteristics of MXenes, including high specific surface areas, active sites, hydrophilicity, environmental-friendly nature, large inter-layer spacing, high chemical stability, and superior sorption/reduction capabilities, position them as ideal candidates for oil/water (O/W) separation applications. This paper critically evaluates the O/W separation mechanisms employed by MXene-based materials, thoroughly explores the regeneration, stability, and durability performance of these materials, and highlights current challenges and research gaps. Furthermore, we present future prospects to overcome these hurdles and advance the field of MXene-based O/W separation technology.