2,2', 4,4'-Tetrabromodiphenyl ether (BDE47) is known as a recalcitrant bromated organic pollutant with the significant persistence, toxicity, and bioaccumulation. In this study, a synergistic effect of ball-milled Al particles with vitamin B-12 on the degradation of BDE47 was found according to the coordinated catalytic reduction process. The micro-scale Al particles prepared by ball milling and vitamin B-12 as common pharmaceutical composed a new combination reagent for hydrodebromination with low-cost and high reactivity. The degradation conditions were optimized by the addition of 2.0 g/L BM Al particles and 0.3mM VB12 using the solvent of methanol/H2O (v: v= 40: 60) at pH 4.0. More than 97% of 25 mg/L BDE47 was debrominated into lower-brominated diphenyl ethers in a sequential pattern and finally into diphenyl ethers within a 120-min reaction. UV/Visible spectra showed that vitamin B-12 (Co(III)) was reduced to vitamin B(12)s (Co(II)) by the ballmilled Al particles, which possesses super nucleophilic property to associate the carbon atom on C-Br bond and then facilitates the hydrodebromination process of brominated diphenyl ethers. The experimental results can provide basic understanding to identify a reaction process of vitamin B-12/vitamin B-12s for the enhanced reductive debromination of polybrominated diphenyl ethers by ball-milled Al particles, which would be possibly applied to treat soil washing solvent in the field of soil remediation.