A novel electroactive α-ZrP/PANI hybrid film with cation exchange property was synthesized by electrochemical method in aqueous solution. The electrochemically switched ion exchange capacity of this film was investigated in 0.1 M Pb(NO₃)₂. The α-ZrP/PANI hybrid films with different structures were prepared on carbon nanotubes (CNTs) and PANI nanofibers modified Au electrodes. The fabrication process and formation mechanism were analyzed by electrochemical quartz crystal microbalance (EQCM). The results shows that the hybrid film prepared on PANI fibers exhibited higher ion exchange capacity because of its three-dimensional porous structure; The P-OH of α-ZrP not only provides protons for the redox of PANI but also shows adsorption selectivity for Pb₂ , which makes this hybrid film perform good electroactivity in neutral solution containing Pb₂ . Therefore, this hybrid film could be served as an ESIX material for separation and recovery of Pb₂ by controlling the oxidation-reduction of hybrid film.