A two-stage process has been developed for the separation of o-/p-hydroxyacetophenones (o-/p-HAP), both of which are intermediates for the pharmaceutical industry. The first step is the selective solubilization in a hydrocarbon solvent; o-HAP dissolves well in heptane and toluene, but p-HAP does not. The intermolecular hydrogen bonding among p-HAP molecules makes it almost insoluble in heptane and has solubility in toluene as low as 0.03 mol/kg of solvent. The first step gives a hydrocarbon solution of o-HAP with a very small amount of dissolved p-HAP, while pure p-HAP precipitates as a solid in high yield (similar to90%). The traces of p-HAP from the organic solution can be removed in the second step using its selective sorption in weakly basic resins, giving a solution with o-HAP. The sorption of p-HAP on the resins by acid-base interactions between the resin's amino group and p-HAP's acidic hydroxy group is aided by the unfavorable solvation of p-HAP in the organic phase.