The development of easily separated from water, high effective mineral ion removal materials is quite required in the hard water treatment system. In this study, water-stable polyelectrolyte polyacrylic acid (PAA) nanofibrous mats were fabricated by electrospinning technology and subsequent thermal crosslinking. Influence factors such as contact time, mat content, temperature and interfering ions strength were experimentally examined. The results indicated that polyelectrolyte PAA nanofibrous mats could be used as high effective Ca(II) ions removal material via complexation to form PAA-COOCa2+ complex, with a maximum Can ion removal capacity of 152.8 mg/g within 60 min at 25 degrees C. Both equilibrium and kinetic studies showed that the behaviors of Ca(II) ions removal by polyelectrolyte nanofibrous mats followed Freundlich model and fitted pseudo-second-order model, respectively.