A new on-line technique for the analysis of complex petroleum samples is presented employing a microbore high-performance liquid chromatography (HPLC) system for first-stage fractionation by ring size, directly coupled to a high-resolution capillary gas chromatography (GC) system for isomer separations, followed by an on-line mass spectrometer for identification. The use of microgore HPLC and a newly developed low-dispersion stream splitter permitted non-discriminative transfer of the fractionated LC zones directly to the gas chromatograph without the need for further LC miniaturization or retention-gap techniques on the gas chromatograph. The eluent splitter also allowed the simultaneous monitoring of the eluent for accurate zone sampling and transfer, and for the introduction of further separation dimensions such as LCLCGC—mass spectrometry (MS). The LCGCMS was applied to a solvent refined coal sample with the three- and four-ring fractions being separated and identified. Probability of the LCGC system to separate pure components ranged from 95 to 97% for the coal tar sample vs. to 7.0% for a single-stage, capillary GC separation.