The catalysis of the hydroesterification and hydroformylation-acetalization of 1-hexene by rhodium(I), cis-[Rh(CO)2(amine)2](PF6) complexes (amine = pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-lutidine or 2,6-lutidine) dissolved in 10 mL of ethanol or 10 mL of 80% aqueous ethanol, 0.4 mL (3 x 10-3 mol) of 1-hexene, [Rh] = 5 x 10-5 mol, 1-hexene/Rh = 64 under P(CO) = 0.9 atm at 100 °C for 4 h, is described in this work. The mayor products are ethyl-heptanoate, heptanal and 1,1-diethoxyheptane coming from the hydroesterification, hydroformylation reactions and the nucleophilic addition reaction of the ethanol over the formed heptanal, respectively. The reaction product distribution depends on the nature of the coordinate amine to the rhodium center