Genotoxic nitrosamine impurities have increasingly posed substantial safety concerns for pharmaceutical formulations, particularly sitagliptin/metformin combination tablets. In particular, <i>N</i>-nitrosodimethylamine (NDMA) and 7-<i>N</i>-nitroso-3-(trifluoromethyl)-5,6,7,8-tetrahydro[1,2,4]triazolo[4,3-<i>a</i>]pyrazine (NTTP)-a newly identified nitrosamine drug-substance-related impurity (<i>N</i>-nitroso-sitagliptin or <i>N</i>-nitroso-STG-19)-have been detected in these pharmaceutical formulations. However, there are no established analytical methods addressing the simultaneous quantification of these two distinct classes of nitrosamine impurities in a single analysis. Therefore, we aimed to develop and validate a robust analytical approach utilising liquid chromatography-mass spectrometry (LC-MS) coupled with atmospheric-pressure chemical ionisation (APCI). Comparison of the ionisation modes and mass analysers revealed that LC-APCI-MS significantly outperformed electrospray ionisation for NDMA, whereas both ionisation methods were suitable for NTTP. Furthermore, both high-resolution quadrupole time-of-flight and triple quadrupole mass spectrometry platforms met the regulatory validation criteria, with excellent linearity (<i>R</i>² > 0.997), recovery (95-102%), and precision (RSD < 5.7%) observed across both instruments. In contrast, GC-MS analysis, one of the major methods for NDMA or nitrosamine detection, was unsuitable for NTTP quantification because of inadequate volatility and chromatographic resolution. As sitagliptin/metformin remains the primary therapy for type 2 diabetes, the proposed method offers a practical solution for quality control monitoring and ensures a safe and stable supply of this widely used combination product.