Summary: Poly(acryloamidino ethyleneamine) (PAEA) and poly(acryloamidino diethylene diamine) (PADD) have been synthesized for the observation of CuII complex and Cu(OH)2 crystal‐growth on the surface of different numbers of amino groups immobilized on polyacrylonitrile (PAN) fibers. The shape of CuII crystal growth depends on the amine chain length of the chelating fiber; Cu(OH)2 crystals grow on the surface of the chelating fiber after CuII adsorption.