In order to recycling adsorbent of wastewater, magnetic adsorbents with recycling properties were prepared by fly ash magnetic powder (CMS)-doped polyaniline microfiber composites (CMS/PANI microfiber). The cheap fly ash magnetic powder is obtained from industrial solid waste fly ash. XRD patterns of CMS/PANI microfiber shows that the peaks at 30o are corresponding to the magnetite in CMS. SEM images shows that CMS/PANI fibrous winding structures forming a porous cage, where microfiber have the diameter of 60 nm and the length of 2-3 um. EDS spectra indicated that the magnetic dots monodispersed on the surface of every root of microfiber. BET surface areas of PANI microfiber and CMS/PANI microfiber are 36.42 m2/g and 25.75 m2/g, respectively. The different wastewater samples has been used including congo red(CR), methyl orange(MO) and halogenated element ions solutions. The maximum adsorption amounts of CR and MO were 324.68 mg/g and 212.3 mg/g, respectively. Interestingly, the CMS/PANI nanofibre material still adsorbs very well to other ionic wastewaters. The magnetic adsorbent achieves a sorption rate of 70% for Ca2+ containing wastewater under certain conditions. The magnetic adsorbent exhibited 48% adsorption of Cl- and over 90% adsorption of F-, Br- and I-. After six cycles of magnetic separation, the adsorption rate was still above 96%. The adsorption curves and equation fits show that the adsorption process is consistent with the langmuir isotherm model and the quasi-secondary kinetic model.