A decomposition process for PCBs by using basic molten salts as a reaction field was investigated in order to establish a safe, simple and highly efficient decomposition process for polychlorobiphenyls (PCBs). PCB containing chlorine (e.g. 2, 2×, 4, 4×-tetrachlorobiphenyl) dissolved in n-nonane solution was supplied into basic molten salts (NaOH-Na2CO3 or KOH-K2CO3) maintained at 500-700°C together with the carrier gas (N2-21% O2) through an injection tube. The injected PCBs in a bubble are decomposed by the reaction with the molten salts and oxygen during rise in the molten salts. The decomposition efficiency of PCBs increased with increasing temperature and was achieved to be higher than 99.995% in a certain condition. From a series of systematic study, the effectiveness of the decomposition process for PCBs by using molten salts was demonstrated.