The formation of carcinogenic N-nitrosamines from reactions between solvent amines and flue gas NOx is an important concern for the application of amine-based processes to capture CO2 post-combustion. Using an advanced test rig with interconnected absorber and desorber units, we evaluated the importance for N-nitrosamine formation of the desorber relative to the absorber, and any synergism between the two units. Variations in desorber temperature and in flue gas composition indicated that N-nitrosamine formation from fresh monoethanolamine (MEA) occurred predominantly in the absorber. N-nitrosamine formation was driven by high NO2 and O2 flue gas concentrations, although NO also contributed. In contrast, N-nitrosamine formation from piperazine (PZ) was driven by reactions with nitrite in the heated desorber, and accelerated concurrent with nitrite accumulation. A complementary experiment simulating aged MEA solvent (high nitrite, 1.5% sarcosine as a proxy of secondary amine degradation products) suggested the desorber becomes an order of magnitude more important than the absorber for N-nitrosamine formation. For fresh MEA solvent, increasing the desorber temperature from 110 °C to 130 °C promoted thermal decomposition of N-nitrosamines, reducing N-nitrosamine accumulation rates two-fold. Compared to the test rig, the prevailing practice of using separate absorber columns and autoclave-like treatments to mimic desorber units predicted the direction, but underestimated the magnitude of N-nitrosamine formation. Because N-nitrosamine accumulation rates are the net result of competing formation and thermal decomposition processes, use of continuously cycling test rigs may be necessary to understand the impacts of different operating conditions.