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Since the discovery of microemulsions, they have attracted great attention due to its unique properties, such as ultra-low interfacial tension and nanoscale droplets. During the past several decades, microemulsions have shown unparalleled advantages in critical metal separation and recovery, e.g., high separation rate, high recovery efficiency, and good selectivity. Therefore, fundamental understandings of such metal recovery behavior are of great significance for the continuous development of microemulsion-based separation technology in this field. Herein, we first systematically reviewed the application of regular microemulsion in the separation and recovery process of critical metals focusing on their separation mechanisms. Then, we summarized the recent progress of CO 2 -responsive microemulsions and highlighted their potential application in critical metal separation and recovery, aiming to provide some insights into alleviating the difficulties in demulsification during the stripping stage using regular microemulsions. In this section, the latest development of CO 2 -responsive microemulsions is introduced, and the relationship between their composition, microstructure and macroscopic properties is discussed. Discussion and future perspectives are provided highlighting the design of new microemulsions and potential application of CO 2 -responsive microemulsions for metal separation and recovery in the future. [Display omitted] • Microemulsions for critical metal recovery were summarized focusing on mechanisms. • The latest development of CO 2 -responsive microemulsions was introduced. • Future perspectives of microemulsions for metal recovery were discussed. • Potential use of CO 2 -responsive microemulsions for metal recovery was explored. [ABSTRACT FROM AUTHOR]