The hydrodechlorination of chlorobenzene to benzene and biphenyl was studied using poly(4-vinylpyridine)-immobilized Cu catalysts under CO in basic (NaOH, N(C2H5)(3) or Na(CH3CO2)) aqueous 2-ethoxyethanol medium. This Cu system also catalyzed the water gas shift reaction. The catalytic activities for hydrodechlorination of chlorobenzene to benzene were studied as functions of the reaction parameters (nature of the base, reaction time, [Cu], P(CO), T, and S/C). Among the different base studied activity is maximum for NaOH. The rate of benzene formation displays a first-order dependence on [Cu] over the range 1.25-12.50 wt%. This observation was interpreted in terms of the presence of active species having the same nuclearity. The catalytic activity towards benzene formation proved to be first order dependence on P(CO) over the range 5-35 atm. The kinetics behavior with respect to P(CO) leads to the proposal that CO addition to the catalytic species precedes the rate-limiting step. The catalytic activity proved to be non-linear in chlorobenzene/Cu content, over the range 50-400 molar ratio. The results suggest that the rate-limiting step is preceded by reversible oxidative addition of chlorobenzene to Cu immobilized species.