The　MOF-5@clinoptilolite　(MOF@CP)　composites　are　successfully　synthesized　using　polyvinylpyrrolidone　(PVP)　for　adsorption　separation　of　CO2/CH4,　CO2/N2,　and　CH4/N2.　The　effects　of　the　PVP　amounts　on　the　dispersity　of　MOF-5　on　CP　random　lamellas　of　the　MOF@CPs　are　evaluated　via　various　characterizations.　Meanwhile,　their　single-component　gas　adsorption　isotherms,　breakthrough　experiments,　and　cycling　test　are　measured.　The　results　elucidate　that　the　used　PVP　amount　has　a　significant　influence　on　the　particle　size　and　the　uniformity　of　MOF-5　dispersed　on　CP　random　lamellas.　The　MOF-5-loaded　amount　in　MOF@CP　is　estimated　to　be　up　to　42.52 wt.%.　Especially,　the　surface　fractal　evolutions　indicated　the　surfaces　of　MOF@CP　became　from　rough　to　smooth　with　the　increase　of　PVP.　The　CO2/CH4,　CO2/N2,　and　CH4/N2　selectivity　factors　of　MOF@CP　are　higher　than　that　of　CP,　displaying　a　better　separation　performance.　Their　cycling　test　revealed　that　MOF@CPs　could　be　used　repetitively,　highlighting　efficiency　for　CO2　and　CH4　separation.　Meanwhile,　the　MOF-5@CP　stability　under　moisture　is　preliminarily　investigated,　showing　higher　moisture　resistance　stability　than　MOF-5.　Additionally,　the　grand　canonical　Monte　Carlo　simulations　demonstrated　the　adsorption　separation　mechanism　of　the　prepared　MOF@CPs.　©　2024　Wiley-VCH　GmbH.