The applicability of linear solvation energy relationships (LSERs) to reversed-phase liquid chromatography (RPLC) was studied by examining the retention of a wide variety of aliphatic and aromatic compounds over the range of 20-50% (v/v) acetonitrile, methanol and tetrahydrofuran. The role of cavity formation, dispersion interaction, polarity/polarizability, hydrogen bond acidity, and hydrogen bond basicity in determining the retention behavior as the mobile phase composition was changed has been investigated. The LSER coefficients were then examined in terms of the corresponding properties of the mobile phase (cohesive energy density, surface tension, the Abraham solvophobic parameter, polarity/polarizability, hydrogen bond basicity, and hydrogen bond acidity) and from these the influence of mobile phase and stationary phase on the retention behavior was explored, in order to chemically interpret the RPLC retention results we compared them to alkane-water and octanol-water partition coefficients. (C) 1998 Elsevier Science B.V.