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The unique properties of MXenes have been deemed to be of significant interest in various emerging applications. However, MXenes provide a major drawback involving environmentally harmful and toxic substances for its general fabrication in large-scale production and employing a high-temperature solid-state reaction followed by selective etching. Meanwhile, how MXenes are synthesized is essential in directing their end uses. Therefore, making strategic approaches to synthesize greener, safer, more sustainable, and more environmentally friendly MXenes is imperative to commercialize at a competitive price. With increasing reports of green synthesis that promote advanced technologies and non-toxic agents, it is critical to compile, summarize, and synthesize the latest development of the green-related technology of MXenes. We review the recent progress of greener, safer, and more sustainable MXene synthesis with a focus on the fundamental synthetic process, the mechanism, and the general advantages, and the emphasis on the MXene properties inherited from such green synthesis techniques. The emerging use of the so-called green MXenes in energy conversion and storage, environmental remediation, and biomedical applications is presented. Finally, the remaining challenges and prospects of greener MXene synthesis are discussed.