Abstract This study reports the synthesis of three novel polyacrylonitrile (PAN) nanofibers based calixamide containing pyridine groups by electrospinning. The structures of the newly prepared nanofibers were clarified using spectroscopic techniques. Analysis indicated that preparation of nanofibers based calixamide was successfully achieved. The presence of calixarene molecules in the nanofiber backbones was confirmed by Fourier transform infrared (FTIR-ATR), scanning electron microscope (SEM), and thermogravimetric analyses (TGA and DSC). The toxic anion binding studies exhibited that the nanofiber-based calixamide could be efficiently used for the binding of chromate anions as a model toxic oxoanion. Nanofiber based calixamide may be a good candidate as a filter material for water purification and waste treatment owing to their very large surface area as well as the inclusion complexation capability of all surfaces associated with the calixarene skeleton.