Shewanella oneidensis MR-1 (MR-1)-impregnated alginate capsules with 3D porous structure were prepared through cation crossing-linking and was used for the Cr(VI) reduction and removal. After being encapsulated by alginate, the endurance of the MR-1 was largely enhanced under conditions of high Cr(VI) concentrations (up to 4 mM) and low pH (pH 5). The Cr(VI) reduction over the MR-1-impregnated alginate capsules could be fitted by pseudo first-order kinetic model. With the Cr(VI) initial concentration increasing from 1 to 4 mM, the first-order rate constant for the encapsulated MR-1 (kcapsules) and free cells (kcells) fell by 26.3% and 82.4%, respectively. At pH 5, the kcapsules value was 0.19 h- 1, which was about 3.7 times higher than kcells. Moreover, the encapsulated MR-1 held 90.5% of the Cr(VI) reduction ability after 15 days of resting time, while the free MR-1 held 19.7%. After bioreduction, 73.6% of total chromium was adsorbed on the MR-1 impregnated Ca-alginate capsules. XPS results showed 85% of the adsorbed chromium was Cr(III). The mechanism for chromium removal over the MR-1-impregnated Ca-alginate capsules was proposed with the following steps: (1) Cr(VI) was bioreduced via the encapsulated MR-1; (2) the reduced soluble Cr(III) was adsorbed by alginate selectively. In the study, the Ca-alginate shell of the cabbage-like MR-1 impregnated capsules could be a shelter for encapsulated MR-1 to endure unfavorable conditions (e.g., low pH and high concentration of Cr(VI)) and immobilize the soluble chromium. Considering the obtained capsules derived from biomolecules were environment-friendly, the MR-1-impregnated Ca-alginate capsules were potential for the application in the remediation of environmental pollution. Graphical abstract.