This study illustrates the utility of tetraplex stable isotope coded tags in mass spectrometric glycomics using three carbohydrate classes. The teteraplex tags allow for the direct comparison of glycan compositions within four samples using capillary scale hydrophilic interaction chromatography with online mass spectrometry. In addition, the ability to discern glycan structural isomers is shown based on the tandem mass spectra of each composition using nanospray ionization. Results are shown for chondroitin sulfate proteoglycans, low molecular weight heparins, full length heparins, and N-glycans from alpha-1-acid glycoproteins from four mammalian species. The data demonstrate the value of the tetraplex stable isotope tagging approach for producing high-quality glycomics compositional profiling and fine structural analysis.