The high-temperature reactions of chlorinated hydrocarbons are reviewed with a primary focus on the gas-phase molecular growth chemistry and elementary reaction mechanisms leading to the formation of chlorinated benzenes and chlorinated polycyclic aromatic hydrocarbons. Recent heterogeneous mechanistic studies of the chlorination and condensation of aliphatic hydrocarbons at lower temperatures are also summarized. Copper(II) valent species play an important role as catalyst and reagent. The main thermal pathways for chlorinated dibenzodioxins and furans have been deduced by these laboratory experiments, which try to model the complex reality of the post-incineration zone of municipal and hazardous waste incinerators.