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Characterization of methylenedianiline (MDA) 2-ring isomers (2,2′-, 2,4′- and 4,4′-MDA) is reported using matrix assisted laser desorption/ionization-mass spectrometry (MALDI-MS), a common technique used for characterizing synthetic polymers. MDA is a precursor to methylene diphenyl diisocyanate (MDI) a hard block component in polyurethane (PUR) synthesis. This manuscript focuses on comparing MALDI results to those of our previous electrospray ionization-mass spectrometry (ESI-MS) studies. In ESI, 2-ring MDA isomers formed single unique [M+H]+ (199 Da) parent ions, whereas in MALDI each isomer shows significant formation of three precursor ions: [M−H]+ = 197 Da, [M·]+ = 198 Da, and [M+H]+ = 199 Da. Structures and schemes are proposed for the MALDI fragment ions associated with each precursor ion. Ion mobility-mass spectrometry (IM-MS), tandem mass spectrometry (MS/MS), and computational methods were all critical in determining the structures for both precursor and fragment ions as well as the fragmentation mechanisms. The present study indicates that the [M−H]+ and [M·]+ ions are formed by the MALDI process, explaining why they were not observed with ESI.