Different ionization techniques based on different principles have been applied for the direct mass spectrometric (MS) analysis of crude oils providing composition profiles. Such profiles have been used to infer a number of crude oil properties. We have tested the ability of two major atmospheric pressure ionization techniques, electrospray ionization (ESI(±)) and atmospheric pressure photoionization (APPI(+)), in conjunction with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The ultrahigh resolution and accuracy measurements of FT-ICR MS allow for the correlation of mass spectrometric (MS) data with crude oil American Petroleum Institute (API) gravities, which is a major quality parameter used to guide crude oil refining, and represents a value of the density of a crude oil. The double bond equivalent (DBE) distribution as a function of the classes of constituents, as well as the carbon numbers as measured by the carbon number distributions, were examined to correlate the API gravities of heavy, medium, and light crude oils with molecular FT-ICR MS data. An aromaticity tendency was found to directly correlate the FT-ICR MS data with API gravities, regardless of the ionization technique used. This means that an analysis on the molecular level can explain the differences between a heavy and a light crude oil on the basis of the aromaticity of the compounds in different classes. This tendency of FT-ICR MS with all three techniques, namely, ESI(+), ESI(−), and APPI(+), indicates that the molecular composition of the constituents of crude oils is directly associated with API gravity.