Catalytic hydrodechlorination (HDC) has proved to be an efficient approach to dispose chlorinated organic compounds (COCs). The influence of solvent on the HOC of chlorophenols with H-2 over Raney Ni catalyst was investigated. We found that protic solvents, especially water, significantly accelerated liquid-phase HOC that was sluggish in aprotic solvents. Among the selected solvents, water was the most effective solvent for liquid-phase HDC over Raney Ni catalyst. To study the mechanism for the rate acceleration in the HOC that was promoted by protic solvents, catalysts were characterized by SEM, EDX, and XRD techniques. It was found that solvent could affect surface composition and surface micro-topography of Raney Ni catalyst. On the basis of these studies, an effective and practical reaction system was developed to dispose chlorophenols over Raney Ni catalyst; a broad range of chlorophenols were efficiently hydrodechlorinated in aqueous solutions under mild conditions, and the catalyst could be reused at least five times without any loss of catalytic activity. (C) 2014 Elsevier B.V. All rights reserved.