This paper describes catalytic activation studies of the water-gas shift reaction by cis-[Rh(CO)(2)(amine)(2)]PF6 (amine = 4-picoline, 3-picoline, 2-picoline, pyridine, or 2,6-lutidine) heterogenised on poly( 4-vinylpyridine) in aqueous 2-ethoxyethanol. The effect of varying the nature of the amine was investigated. The rhodium complexes bearing 4-picoline (4-pic) ligands proved to be most active among those surveyed, and displaying turnover frequencies for hydrogen production of 8.9 mol of H-2 per mole of Rh per day for 9.4 x 10(-5) mol cis-[Rh(CO)(2)(4-pic)(2)]PF6/1.00 g poly(4-vinylpyridine), P( CO) = 0.9 atm at 100 degrees C.