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Native mass spectrometry (MS), which involves the detection of intact protein complexes in the gas phase, is an emerging technique for analyzing glycoprotein heterogeneity. In this chapter, we describe the use of the native MS approach to decode the compositional complexity of glycoproteins and to correlate glycosylation features with structural heterogeneity. Moreover, we highlight recent representative applications in connecting glycan heterogeneity with protein complex assemblies and interactions.

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