In order to carry out a comparison, the hydroformylation of 1-hexene to their corresponding aldehydes (heptanal and 2-methyl-hexanal) was studied both under syngas conditions and with paraformaldehyde using the catalytic rhodium/diphosphine precatalysts; the catalytic systems were formed in situ by the addition of one or two equivalents of the corresponding diphosphine, Ph2P(CH2)(n)PPh2, n = 2 (dppe), 3 (dppp) and 4 (dppb), to the carbonyl complex Rh(acac)(CO)(2). For the hydroformylation reactions under syngas conditions, the more active systems were the ones containing one equivalent of the diphosphine, which produce trigonal bipyramidal species like RhH(CO)(2)(diphos). The activity and selectivity of these systems strongly depend on the bite angle of the ligand: when the bite angle increases both parameters are higher (dppb > dppp > dppe). Contrary to these results, for the reaction with paraformaldehyde, the systems containing two equivalents of the diphosphine ligand, which produce the cationic square planar species [Rh (diphos)(2)]+, were more active than those containing one equivalent; the reaction rate decreases with the enlargement of the carbon chain of the bridge between the two phosphorous atoms of the diphosphine (dppe > dppp > dppb). These results may be explained by a higher steric effect on the metal center, which probably produces a decreasing of the rate of the CH2O oxidative addition reactions. For both reactions, these effects were explained through DFT calculations of the corresponding resting states.