Rhodium complexes modified by simple trialkylphosphines can be used to carry out homogeneous hydroformylation in supercritical carbon dioxide (scCO(2)). The catalyst derived from PEt3 is more active and slightly more selective for the linear products in scCO2 than in toluene, and under the same reaction conditions [100degreesC, 40 bar of CO/H-2 (1:1)] P(OPri)(3) is also an effective ligand giving good catalyst solubility and activity. Other ligands such as PPh3, POct(3), PCy3, and P(4-C6H4But)(3) are less effective because of the low solubility of their rhodium complexes in scCO(2). P(4-C6H4SiMe3)(n) Ph3-n (n = 3 or 1) and P(OPh)(3) impart activity despite their complexes only being poorly soluble in scCO(2). Under subcritical conditions, using PEt3 as the ligand, C7-alcohols from hydrogenation of the first formed aldehydes are the main products whilst above a total pressure of 200 bar, where the solution remains supercritical (monophasic) throughout the reaction, aldehydes are obtained with 97% selectivity. High pressure IR studies in scCO(2) using PEt3 as the ligand are reported.