An experimental method was developed and validated for the collection and analysis of tobacco-specific nitrosamines (TSNAs) that are present in electronic cigarette (EC) liquid or are released from aerosol samples using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system. As part of this study, the relative recovery of four target TSNAs was assessed by spiking standards in a mixture of propylene glycol and vegetable glycerin. Recovery was assessed against two major variables: (1) the chemical media (solution) selected for sample dilution (acetonitrile [ACN] vs. ammonium acetate [AA]) and (2) the type of sampling filter used (Cambridge filter pad [CFP] vs. quartz wool [QW] tube). The average recovery of TSNAs in terms of variable 1 was 134 ± 22.1% for ACN and 92.6 ± 8.27% for AA. The average recovery in terms of variable 2 was 83.4 ± 7.33% for QW and 58.5 ± 12.9% for CFP. Based on these conditions, the detection limits of N′-nitrosonornicotine (NNN), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), N′-nitrosoanatabine (NAT), and N′-nitrosoanabasine (NAB) were calculated as 4.40, 4.47, 3.71, and 3.28 ng mL−1, respectively. The concentration of TSNAs in liquid and aerosol samples of six commercial EC solutions was measured as below the detection limit.