Selectivity and product distribution of hydrodechlorination (HDCl) of dieldrin and DDT are studied in different liquid phase systems, namely in: (1) in ethanol; and (2) in the supported ionic liquid heterogeneous catalytic system (multiphase system), composed by the organic phase and aqueous KOH, a quaternary ammonium ionic liquid promoter (Aliquat 336), and a metal catalyst, e.g. 5% Pd/C, 5% Pt/C, or Raney-Ni. At 50 degreesC and atmospheric pressure of hydrogen, a quantitative hydrodechlorination of DDT in the biphasic system with ionic liquid layer is achieved in 40 min and in 4 h with Raney-Ni and Pd/C, respectively, while the reaction on Pt/C or on Pd/C without Aliquat 336 is slow. Dieldrin undergoes partial dechlorination, with high selectivity achievable only for its mono- and bi-dechlorination products. Dechlormation pathways and reactivity of different types of organic chlorine atoms versus the catalyst nature and other conditions are discussed. (C) 2004 Elsevier B.V. All rights reserved.