Food emulsions are complex colloidal systems whose structural and molecular properties critically influence stability and sensory attributes. This study combines cryogenic time-of-flight secondary ion mass spectrometry (cryo-ToF-SIMS) with transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM) to characterize the chemical and structural properties of bovine milk, cream, and an oat-based cream analogue. Cryo-ToF-SIMS enabled parallel mapping and spatial correlation of multiple molecular components, including fat, proteins, calcium, phospholipids and sugars, in microscopic structures, such as fat globules and interstitial elongated aggregates, which were structurally characterized at the nanometer level with TEM. ToF-SIMS correlation analysis revealed significant differences in the molecular composition of the interstitial aggregates, with considerably less mixing of components in the oat-based cream analogue. In addition, 3D analysis of individual milk fat globules generated depth profiles of calcium and proteins at the surface of fat globules, consistent with casein binding to the surface of the protein-containing milk fat globule membrane (MFGM). Furthermore, the triglyceride content of the fat globules were characterized using mass spectra from ToF-SIMS and found to be consistent with the reported fatty acid distributions in Swedish cow milk for bovine milk and cream, and in rapeseed oil for oat-based cream analogue