Reported here is the catalytic studies of the hydroformylation and the isomerization of 1-hexene to aldehydes (heptanal and 2-methyl-hexanal) and 2-hexene, respectively by [Rh(COD)(amine)2]PF6 complexes (COD = 1,5-cyclooctadiene, amine = 4-picoline, 2-picoline or 2,6-lutidine) immobilized on poly(4-vinylpyridine) in contact with 10 mL of 80% aqueous 2-ethoxyethanol, under CO atmosphere (0.9 atm at 100 C). The results of these studies show the following reactivity order defined as Turnover Frequencies for aldehydes production: 2-picoline {2.9} > 4-picoline {2.6} > 2,6-lutidine {2.4}. The electronics and steric effects induced by the amine ligands apparently influence on the observed catalytic activities. The [Rh(COD)(2-picoline)2]PF6/poly(4-vinylpyridine) system also catalyzed the hydroformylation and isomerization of 1-octene