In this work, we prepared amidoxime-functionalized polyacrylonitrile (APAN) micro/nanofibers by modifying solution-blown PAN fibers with hydroxylamine hydrochloride, and investigated the adsorption performance of the APAN fibers for Cd(II), Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) from aqueous solutions. Batch experiments and quantitative analysis were conducted considering initial pH and contact time as controlling parameters. The equilibrium data were better explained by the Langmuir model with maximum adsorption capacities of 185, 204, 105, 104, 345 and 91 mg/g for Cd(II), Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The adsorption kinetics were found to follow the pseudo-second-order kinetic model. The calculated thermodynamic parameters demonstrated that the adsorption of metal ions onto APAN fibers is feasible, spontaneous and endothermic. The five adsorption–desorption cycle experiments showed that APAN micro/nanofiber adsorbent exhibits good reusability, and has a potential application for the removal of heavy metals from wastewater.