A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOFMS) method has been developed for separation of a series of petroleum samples using a polar/non-polar column set configuration. Groups of oils were selected to provide samples from the same oil family to assist in comparison of compositional changes during biodegradation. The groups also represented different sources and ages to allow an assessment of the application of GC x GC for the differentiation of oil source, as well as fluid history. The increased resolution and separation afforded by the GC x GC technique provides more complete compositional information on complex biodegraded oil samples than one-dimensional GC, and improves the ability to study biodegradation trends. Among the components identified, it is proposed that alkyl-decahydronaphthalenes constitute a significant contribution to the UCM.