Batch test was conducted to investigate Se(IV) removal kinetics and mechanism by zero valent iron (ZVI) in presence of Fe(II) under anaerobic condition. Dissolved Fe(II) activated and enhanced Se(IV) reduction by ZVI, which also determined the removal efficiency, reduction rate, final corrosion products and their structures. Se(IV) was completely removed at initial Fe(II)/Se(IV) ≥ 1.0, and the specific rate constant significantly increased from 0.6 to 3.44 L h-1 m-2 with the augment of ratio from 1.0 to 1.4. At Fe(II)/Se(IV) < 1.0 (take 0.6 as an example), Raman, XPS, SEM-EDS and XRD results suggested that Se(IV) was reduced to amorphous Se(0) in forms of red suspended solids, amorphous FeSe and crystal maghemite (γ-Fe2O3) coated on ZVI surface. At Fe(II)/Se(IV) ≥ 1.0 (take 1.0 and 1.4 as examples), crystal FeSe and magnetite (Fe3O4) deposits formed on ZVI surface with a core-shell structure. Additionally, final pH increased due to Se(IV) reduction. This study suggested that traditional ZVI passivation problem could be overcome through the addition of excess dissolved Fe(II) under anaerobic condition, which also provided an alternative method to produce a reactive ammonia-free Fe3O4/ZVI/Fe(II) system.