It is well recognized that lipophilic factors play a significant role in the correct understanding of a great many pharmacochemical and xenobiotic problems. The rapidly growing interest in reliable parameters describing hydrophobic features accelerated the search for suitable alternatives of the rather tedious classic shake-flask method. High-performance liquid chromatography (HPLC) especially has developed into an indispensable technique. The present paper compares classic log P values (as far as available) and calculated ϵf values of polymethyl- and polychloro-derivatives of benzene and biphenyl (including some fluoro-, bromo- and iodo-derivatives) with their HPLC data and discusses in some detail steric hindrance of resonance and hydration in biphenyl structures. We found that the application of normal-phase silica gel columns may provide substantial information on non-hydrophobic binding of aromatic ring systems to suitable carriers, e.g. proteins and receptors.