The potential effect of base on Raney Ni-catalyzed hydrodechlorination (HDC) of chlorophenol was studied. Compared to weak inorganic bases, strong inorganic bases (NaOH and KOH) and triethylamine (EtN) were more favorable to promote Raney Ni-catalyzed HDC reaction. Moreover, a stoichiometric amount of NaOH/EtN was found to be optimal for the HDC reaction, and up to 100% conversion of 4-chlorophenol was achieved within 30 min. Catalyst characterization (SEM, EDXS, and XRD) combined with ICP-OES analysis were introduced to better understand the mechanism for the promoted effect of base on the HDC reaction. The results showed that the optimal amount of strong inorganic bases and EtN efficiently eliminated HCl corrosion to Raney Ni, greatly reduced the active phase Ni and Al leaching, and avoided collapse of the catalyst framework. Based on the mechanism, the best bases and their optimal amount were developed for further disposal of polychlorinated phenols, and excellently stepwise HDC of polychlorinated phenols was achieved. Recycling tests showed that Raney Ni could be reused at least 5 times for the HDC reaction with the stoichiometric amount of NaOH, which was a promising option for the HDC of wastewater containing chlorophenols over Raney Ni.