The reactive extraction of aldehydes from aqueous solutions with primary amine Primene JM-T was explored. The extraction capability of Primene JM-T towards several aldehydes with different molecular structure, ranging from straight chain or branched, saturated or unsaturated aliphatic to aromatic and heterocyclic is investigated. The influences of the process parameters such as initial concentration of both amine and aldehydes as well as the effect of temperature on the extraction equilibrium are investigated. In addition, a simple model incorporating both physical and chemical equilibrium is developed to describe the experimentally observed behaviour. It is noticed that higher initial concentration of the amine results in a higher overall distribution ratio, while for a higher initial concentration of aldehyde, the distribution ratio is lower. The overall extraction performance of the Primene JM-T depends highly on the molecular structure of the aldehyde. It decreases in the following order: pentanal > 3-methylbutanal > benzaldehyde > furfural > 2-methyl-2-butenal. It is observed that the temperature effect on the distribution coefficient is highly dependent on the system studied. © 2009 Elsevier B.V. All rights reserved.