Four tetrols of benzo[a]pyrene-DNA adducts were separated using reversed-phase high performance liquid chromatography. Chromatographic fractions containing a given tetrol were readily characterized with solid-matrix room temperature luminescence techniques. Solid-matrix fluorescence and phosphorescence spectra at picogram amounts of a tetrol were easily obtained. Tetrol fractions collected based on retention time, but with no response from the ultraviolet detector, were characterized by solid-matrix luminescence spectra at very small quantities.