The hydroformylation of beta-caryophyllene, one of the most widespread sesquiterpenic compounds, represents an attractive entry to new fragrant compounds. Although apparently facile, it resulted to be quite intricate. beta-Caryophyllene showed no reactivity in a non-promoted rhodium system so that the addition of phosphorus ligands was necessary for the reaction to occur. Bulky monophosphites, the ancillaries usually helpful in the hydroformylation of sterically encumbered double bonds, resulted to be of a little efficiency as they promoted the isomerization of beta-caryophyllene. In spite of these challenges, the catalytic systems and reaction conditions were selected to allow the yields of up to 70% for the major aldehyde under mild conditions. employing a cheap ligand (PPh3) as the promoter and environmentally benign ethanol as the solvent. (C) 2016 Elsevier B.V. All rights reserved.