A thermomorphic approach to rhodium-catalyzed biphasic hydroformylation of higher olefins (C > 6) has been developed based on HRhCO(PPh3)(3)/P(OPh)(3)/propylene carbonate/n-heptane catalytic system. The catalyst system showed excellent selectivity toward the desired linear aldehyde (n/i ratio > 8) and high catalytic activity demonstrated by the efficient recycling without significant loss of the catalyst activity. The effects of the temperature, the total pressure, the ratio of CO/H-2, the reaction time and the type of ligand have been thoroughly studied. (c) 2006 Elsevier B.V. All rights reserved.