Quantifying sphingomyelin (SM) species by infusion-based mass spectrometry (MS) is complicated by the presence of isobaric phosphatidylcholine (PC) species, which generate a common m/z 184 product ion in the presence of ammonium ions as a result of the phosphocholine headgroup. Lithium ion adducts of SM undergo a selective dehydration [Li + H 2 O + (CH 3 ) 3 NC 2 H 4 PO 4 ] with a corresponding neutral loss of −207 Da. This neutral loss was employed to create a SM-selective method for identifying target species, which were quantitated using multiple reaction monitoring (MRM). SM-selective fragments in MS 3 were used to characterize the sphingosine base and acyl chain. These methods were used to identify 50 individual SM species in bovine milk ranging from SM 28:1 to SM 44:2, with d16:1, d17:1, d18:1, d19:1, and d20:1 bases, and acyl fatty acids ranging from 10 to 25 carbons and 0−1 desaturations. Spiked SM standards into milk had a recovery of 99.7%, and endogenous milk SM had <10% coefficient of variation for both intra-and interday variability, with limits of detection of 1.4−5.55 nM and limits of quantitation of 11.8−178.1 nM. This MS−MRM method was employed to accurately and precisely quantify SM species in dairy products, including bovine-derived whole milk, half and half, whipping cream, and goat milk.