The huge variety of mycotoxins requires mass spectrometric approaches as they are applied to metabolomics in its targeted and non-targeted analytical forms. For quantitation of mycotoxins in targeted metabolomics, liquid chromatography coupled to triple quadrupole, Orbitrap™ or time-of-flight mass spectrometers provide accurate results. For identification in non-targeted metabolomics, combinations of UPLC and high resolution mass spectrometry (HRMS) are desirable, but mass resolution is compromised by the mass analyzer's scan rates, required for UPLC. In this review, the application of Orbitrap™, time-of-flight and FT-ICR-MS techniques to mycotoxin research is covered and compared to each other. A superior advantage of all HRMS instruments is that they allow a retrospective data treatment thus preserving the information for later reprocessing. Up to date, ultra high resolving FT-ICR-MS is the only method to unequivocally assign elementary sum formulae but cannot be coupled to UPLC without losing resolution power.