Abstract. Supersonic jet spectroscopic detection has been successfully coupled to capillary supercritical fluid chromatography by introduction of the supercritical effluent into a secondary flow of argon, before supersonic expansion of the combined flow through a converging nozzle. At pressures of 6-10 atm, the flowing sheath of argon efficiently carries eluting sample through a 25-p,m nozzle orifice into the supersonic jet. Dead volumes are negligible in this arrangement, and high-resolution fluorescence excitation spectra are obtained. Perylene and benzo[a]pyrene were selectively detected in a standard reference coal tar sample at detection limits of 150 pg and 5 ng, respectively.