In the present work we report the effect of monoethanolamine (MEA) in the biphasic hydroformylation of the olefin content in a real light naphtha cut from "El Palito" refinery in Venezuela using the Rh/TPPTS system. It was found that the MEA increased dramatically the solubility of a 1:1 mixture of H-2: CO up to 27% compared with pure water which resulted in a 10 fold increase in the reaction rate. There was spectroscopic evidence of the coordination of the MEA to the rhodium centre. This accelerated reaction allowed for the redesign of a pilot-scale naphtha hydroformylation plant with 55% smaller reactors. The aldehydes obtained were predominantly C7 branched with high octane-value, evidencing that the biphasic reaction is a green technological alternative to the toxic additive currently use in gasoline formulations such as TAME and MTBE. (C) 2014 Elsevier B.V. All rights reserved.