Herein, calixarene molecules containing piperidine units at lower rim or upper rim of calix skeleton was turned into a water resistant composite nanofiber adsorbent using polyacrylonitrile (PAN) polymeric support via electrospinning process. The PAN based calixarene nanofibrous adsorbents showed an excellent adsorption capacity toward the toxic chromate anions in aqueous solution. Furthermore, this new nanofiber mats would be promising filter materials for drinking water purification.