To date, collision-induced dissociation and methods based on electron transfer dissociation are considered the standard approaches for the mass spectrometry analysis of N- and O-glycopeptides, respectively, allowing for identification of both peptide and glycan compositions. In recent years, alternative fragmentation methods such as ultraviolet photodissociation (UVPD) and more energetic versions of electron-based techniques (such as electron ionisation dissociation, EID) have been shown to be useful for the analysis of glycopeptides, producing rich information on the glycopeptide structure, including types of glycosidic linkages. We performed a series of LCMS (liquid chromatography coupled with mass spectrometry) experiments to assess the efficacy of UVPD, EID, and electron capture dissociation (ECD) for the analysis of complex glycopeptide mixtures, and we discuss challenges associated with automated analysis of glycopeptide LCMS data.