Diamines have shown promise as CO2 capture solvents, yet very little is known about their pathway for thermal degradation. In this study, diamine thermal degradation was quantitatively monitored in lab-scale experiments on four aqueous diamine solvents; ethylenediamine (EDA) 1,2-propanediamine (1,2-DAP), 1,3-diaminopropane (1,3-DAP) and N-methyl-1,2-ethanediamine (N-MEDA), to gain a more comprehensive understanding of their degradation pathway(s). The major degradation products were identified by high resolution time-of-flight mass spectrometry (TOF-MS). Degradation pathways were proposed showing that the primary thermal degradation route for this class of amine are through carbamate formation followed by intermolecular cyclization to form an imidazolidinone or nucleophilic attack by a free amine to form a diamine urea.