An integrated low-cost alloy and corrosive anion system was attempted to perform aqueous hydrodechlorination (HDC) of biorefractory chlorinated organics. Several influencing factors were investigated for HOC of 2-chlorophenol (2-CP) including anion species, alloy categories, and their dosages. Al-Ni alloy presented the remarkably highest reactivity to remove 2-CP under the action of aqueous fluorine ion (F-) compared with other anions and alloys used in this study. Increasing Al-Ni alloy dosage or initial concentration of F- could enhance of 2-CP HDC efficiency. The optimized results showed that 0.389 mM of 2-CP in solution could be completely dechlorinated into phenol using 10 g L-1 of Al-Ni alloy and 39.7 mM initial concentration of F- within 120-min reaction. The used Al-Ni alloy after each HDC reaction could almost be reactivated to the original activity level of raw Al-Ni alloy for HDC after Ca(OH)(2) treatment to remove the adsorbed species such as AlF3 on alloy surface during three cycle reaction. Moreover, after Ca(OH)(2) activation, F- in the effluent solution could also be effectively removed to under 0.8 mg L-1 due to the formation of insoluble CaF2. The maintenance and regeneration of Al-Ni alloy activity for HDC was mainly attributed to the effects of Ca(OH)(2) activation to remove adsorbed species on Al-Ni surface, inherent structure of alloy with Ni droplets homogeneously dispersed into Al substrate, and the change of its surface morphology with more active sites produced by F- corrosion. (C) 2012 Published by Elsevier B.V.