A host of vanadyl petroporphyrins containing multiple sulfur and oxygen atoms and their combinations (CcH2c+zN4VOoSs = 0-3, o = 1-4, Z = -28 to -70) in a vacuum residue were observed by a combination of extensive enrichment of petroporphyrins and detailed analysis using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Many of the petroporphyrin species are being observed for the very first time. The patterns of the porphyrin type distribution revealed dramatic differences in the sulfur and oxygen atom incorporations and their impact on Z number. For each sulfur atom addition, the average Z-number was reduced by similar to 4-7, implying that sulfur may be incorporated by the additions of thiophene or cyclic thiophene moieties. In contrast, oxygen addition had little to no impact on the average Z number, implying that oxygen may be incorporated as carbonyl or hydroxyl groups. The porphyrin-based structures were found to contain as many as 8 aromatic rings in addition to the porphyrin macrocycle. Petroporphyrins in longer wavelength absorption fractions were found to contain more heteroatoms and more condensed aromatic rings.