Vanadyl porphyrins are detected and characterized by their double-bond equivalents (DBE = number of rings plus double bonds) and carbon number in an unfractionated (raw) asphaltene and unaltered South American crude oil. Atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides the high mass-resolving power (450 000-650 000 at m/z 500) and accurate mass (<300 ppb) to unambiguously assign elemental compositions to each of more than 10 000 peaks in each mass spectrum. Kendrick mass sorting revealed unusually high mass errors for peaks assigned to high DBE O-2 species as well as a suspicious bimodal distribution in plots of DBE versus carbon number for all O-2 species. Inclusion of vanadium in the chemical formula assignment resolved the bimodal distribution into lower DBE O-2 species and vanadyl porphyrins, with a subsequent decrease in mass assignment errors to the same level as those for the thousands of other identified species. Vanadyl porphyrins are detected as both M+ (center dot) and [M + H](+) molecular and quasimolecular ions. Trends in the relative abundance of specific DBE values reveal the structural diversity of the vanadyl porphyrins in the asphaltene and heavy crude oil. To our knowledge, the current results are the first to directly identify and catalog the structural diversity of vanadyl porphyrins directly in raw (unfractionated) asphaltene and unaltered heavy crude oil.