New method was developed to determining ∑β 2 H andπ 2 H descriptors of the linear solvation energy relationship (LSER) with micelle-water partition coefficient obtained using micellar liquid chromatography (MLC). This method was tested with chromatographic data of 20 organic compounds. Good results obtained confirm the validity of the method that opens new possibilities of precise and reliable determination of LSER descriptors of high boiling compounds. This method was used to establish ∑β 2 H andπ 2 H descriptors of 23 polyaromatic hydrocarbons that were not available in the literature.