Solid-phase microextraction has been combined with solid-matrix luminescence for the detection of a variety of compounds at sub-nanogram levels for the first time. Whatman 1PS paper was placed in water solutions of polar and nonpolar compounds for the selective removal of the nonpolar compounds such as benzo(a)pyrene. Distribution constants were obtained for 4-phenylphenol, benzo(f)quinoline, benzo(h)quinoline, phenanthrene, and benzo(a)pyrene. The distribution constants showed that phenanthrene and benzo(a)pyrene in water had a very strong affinity for the 1PS paper. Once the solutes were extracted for a fixed period of time, the 1PS paper was dried, and either the solid-matrix fluorescence or solid-matrix phosphorescence was detected from the adsorbed lumiphors by using the appropriate excitation wavelengths. It was a simple matter to detect at least three adsorbed compounds on the 1PS paper by solid-matrix luminescence. Benzo(a)pyrene was easily detected at a level of 0.02 ng ml(-1) in water. (C) 1998 Elsevier Science B.V.