In this work, a mechanistic study of the hydroxycarbonylation of 1-hexene to heptanoic acid and the water gas shift reaction (WGSR) catalyzed by the rhodium( I) complexes, [Rh(COD)(amine)(2)](PF6) (COD = 1,5-cyclooctadiene, amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized on poly(4-vinylpyridine) in contact with water under CO is discussed. Catalytic cycles for these reactions bearing common Rh-H catalytic species are proposed.