On-line liquid chromatography/mass spectrometry (LC/MS), In combination with low-voltage electron-impact Ionization (LVEI)/medlum-reeolutlon mass spectrometry (MRMS, resolution ~10 000) and advanced data analysis procedures, provides us with an opportunity for In-depth molecular level characterization of high-boiling petroleum or synthetic fuel fractions. This combined technique has been applied to the studies of molecular transformation of a petroleum hydrotreating process on different levels: overall changes of hydrocarbons and heteroatom-contaMng hydrocarbons, compositional changes In terms of compound series, and changes In carbon number distribution within Individual compound series.The usefulness of LC/LVEI/MRMS for unraveling some of the complex chemistry associated with heavy hydrocarbon processes has been demonstrated.