Dechlorination processes attract great interest since they are involved in environmental protection and waste disposal technologies. In this paper, the process of gas-phase dechlorination of 1,2-dichloroethane, chloroform, and chlorobenzene over Ni/Al2O3 catalyst (90 wt% Ni) prepared by a coprecipitation technique was investigated. The reduction behavior of the oxide precursor NiO/Al2O3 was studied by thermogravimetric analysis in a hydrogen medium. A thermodynamic assessment of the conditions under which metallic nickel undergoes deactivation due to the formation of nickel chloride was performed. The dechlorination of chlorinated substrates was studied using a gravimetric flow-through system equipped with McBain balances in a wide range of temperatures (350–650◦C) and hydrogen concentrations (0–98 vol%). The impact of these parameters on selectivity towards the products of hydrodechlorination (C2H4, C2H6, and C6H6) and catalytic pyrolysis (carbon nanomaterial and CH4) was explored. The relationship between the mechanisms of the catalytic hydrodechlorination and the carbide cycle was discussed, and the specific reaction conditions for the implementation of both scenarios were revealed. According to the electron microscopy data, the carbonaceous products deposited on nickel particles during catalytic pyrolysis are represented by nanofibers with a disordered structure formed due to the peculiarity of the process including the side carbon methanation reaction.