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A detailed study of 3-hydroxypropionic acid (3-HP) reactive extraction with tri-n-octylamine (TOA) is proposed for the first time. It aims at uncovering some solvent-solutes interactions and providing global mechanisms to better understand and design the reactive liquid-liquid extraction of 3-HP in a biotechnological process. Eleven solvents of similar molecular sizes and several chemical types (alcohols, esters and alkanes) were investigated to understand their role on the extraction ability. Alcohols were found to be the best solvents thanks to their H-bond donor characteristic and water loading that allowed good solvation of the acid-amine complexes. Further investigations were then undertaken, for n-decanol and oleyl alcohol as solvents, varying acid (0.