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[Display omitted] • Electrospun fibrous membranes of PIMs demonstrate promising performance in water treatment applications. • Electrospun PIMs exhibit a great potential in air filtration applications. • Carbon nanofibers produced from electrospun PIMs show unique advantages in electrochemical applications. • Widespread use of electrospun PIMs in various applications will be possible in the future. Polymers of Intrinsic Microporosity (PIMs) are increasingly recognized as membrane materials for molecular separation applications due to their unique structural and functional properties. Development of electrospun PIMs further improved the practical use of PIM polymers. PIM nanofibers produced by electrospinning could be an effective membrane material to handle various environmental concerns owing to their high surface area, high hydrophobicity and high adsorption abilities. In addition, highly selective electrospun PIMs could be produced by simple modification methods to obtain specific interactions with desired species. Versatility of electrospun PIMs provides a unique advantage of producing various novel fibrous membranes by electrospinning method for a range of potential applications. Therefore, this review aims to discuss the recent progress of electrospun PIMs, their properties and future directions in various applications. [ABSTRACT FROM AUTHOR]