In order to assess the molecular parameters controlling partition coefficients in the di-n-butyl ether/water system, a set of 43 solutes has been selected. Centrifugal partition chromatography and the pi-I-metric method have been used to measure log P-dbe values. Using linear solvation Gibbs-energy relationship analyses, the balance of intermolecular forces governing the di-n-butyl ether partition coefficient has been identified, indicating that the partitioning of H-bond accepters is less important in the di-n-butyl ether/water system than in the n-octanol/water system. The di-n-butyl ether/water system appears to be a valuable substitute to propyleneglycol dipelargolate/water in the detailed characterisation of intermolecular interactions of complex compounds using the (critical quarter) methodology