A scheme of selective removal of metal ions from chromium-containing synthetic solutions with the following chemical composition, Cr (VI)-Fe (III), Cr (VI)-Fe (III)-Ni (II), Cr (VI)-Fe (III)-Ni (II)-Zn (II), and Cr (VI)-Fe (III)-Ni (II)-Zn (II)-Cu (II)) by Shewanella xiamenensis biofilm immobilized on a zeolite support, was proposed. Three biological processes, biosorption, bioaccumulation, and longtime bioreduction, were applied for metal removal. The process of Zn (II), Ni (II), and Cu (II) showed to be pH dependent. The maximum removal of Ni (II) was achieved during a 1-hour biosorption process at pH 5.0–6.0, of Zn (II) at pH 5.0, and of Cu (II) at pH 3.0. Chromium (VI) and Fe (III) ions were more efficiently removed by bioaccumulation. Chromium (VI) removal in the studied systems varied from 16.4% to 34.8 and of iron from 55.8 to 94.6%. In a long-term bioreduction experiment, it was possible to achieve complete reduction of Cr (VI) to Cr (III) ions by Shewanella xiamenensis in 42 days and by Shewanella xiamenensis biofilm on zeolite in 35 days. Shewanella oneidensis can be effectively used to remove metal ions from chemically complex effluents.