Mass spectrometry is a powerful analytical technique, but one of the biggest challenges is in differentiating stereoisomers. Techniques such as NMR and X-ray are good at this, but they typically require pure samples and significantly greater amounts of material than mass spectrometry. We have developed a simple mass spectrometry method that can differentiate pentoses and hexoses, and determine the linkage position and anomericity of disaccharides at nanomolar concentrations in complex mixtures. This presentation will be a saga of the journey from pyrolysis of cellulose to the detection of sugars in e-cigarette liquids. Stops along the way will include some fundamentals of quadrupole ion trap mass spectrometry, metal ion adduction to carbohydrates, ion/molecule reactions, kinetics, and density function theory calculations, with a little serendipity thrown in.