The effects of cations and anions of room temperature ionic liquids (RTILs) on the decomposition of chlorophenols and formation of phenol were investigated by gamma and pulse radiolyses. Absorption bands were observed for aliphatic RTILs just after pulsed electron irradiation, and were assigned as solvated electrons. The decomposition yield of chlorophenol (CP), G(-CP), and the formation yield of phenol, G(Phenol), in RTILs, in which solvated electrons were observed, were higher than those in RTILs, in which the solvated electrons were not detected. G(-CP) and G(Phenol) increased with the viscosity of the RTILs which have diethylmethyl(2-methoxyethyl)ammonium (DEMMA) as cation. G(Phenol) in DEMMA-bis(trifluoromethylsulfonyl)imide (TFSI) having high viscosity was higher than that in trimethylpropylammonium (TMPA)-TFSI having low viscosity. The ratios of G(Phenol)/G(-CP) were not affected by the substituted position of chlorine on CP in RTILs.