Forty-one types of crude oils were divided into the following six groups, based on the analysis of the homologous series of hopanes of 18 alpha-22,29,30-trisnorneohopane (1), 17 alpha-22,29,30-trisnorhopane (2), 17 alpha-21 beta(H)-norhopane (3), oleananes (4), and 17 alpha-21 beta(H)-hopane (5) as biomarkers by GC-MASS, in combination with the inductively coupled plasma-atomic emission spectroscopy (ICP-AES) measurement of nickel and vanadium and X-ray fluorescence spectroscopy (XFS) of sulfur: (a) northern Middle East; (b) eastern Middle East; (c) southern Middle East; (d) Borneo Island, Malaysia, and Vietnam; (e) Sumatra Island, China, Gabon, and Russia; and (f) Mexico crude oils. The relationship between the ratios of 4/5 and 3/5 classified the 41 crude oils into three groups of (d), (e), and (a-c) and (f), which was divided into (a) and (f), (b), and (c), based on the 3/5 and 1/2 ratios. Furthermore, the distribution of vanadium and nickel showed that the Middle East crude oils were subdivided into two groups: the southern parts and the northern parts. The individual Mexican crude oil was differentiated by the determination of the sulfur content of all the crude oils in combination with the vanadium and nickel contents. The crude oils were discriminated based on the hopane analysis in combination with the ICP-AES analysis of nickel and vanadium and XFS of sulfur. This combination method is superior for the identification of crude oils. Two analytical cases of spilled oils and heavy oils provided the discrimination into the individual oils based on the analysis of the hopane series.