As　an　indispensable　substance　to　human　survival,　air　is　contaminated　by　a　variety　of　sources,　such　as　from　industrial　emissions　and　human-living　activities.　Among　the　adsorption/absorption　materials,　electrospun　nanofibers　with　high　specific　surface　area　have　been　counted　as　potential　candidates　for　environmental　protection　or　governance,　especially　for　rapid　capture　of　gas　pollutants.　This　review　presents　the　state-of-the-art　developments　in　rational　design　of　electrospun　nanofibers　for　gas　purification.　Firstly,　the　development　history　and　design　principles　of　electrospinning　technique　are　discussed,　in　order　to　clearly　understand　the　commonly　used　technology.　Secondly,　the　structure　design　methods　and　derived　improvements　typically　based　on　the　original　electrospinning　are　extensively　summarized.　Thirdly,　the　innovative　design　for　composition,　structure,　and　properties　of　electrospun　nanofibers　to　purify　different　gaseous　pollutants　are　extensively　clarified,　including　NOx,　CO,　CO2,　H2S,　VOCs　and　SO2.　Finally,　some　newly　emerging　challenges　and　opportunities　for　constructing　high-performance　electrospun　nanofibers　from　lab　level　towards　practical　applications　are　illustrated.