In this study, we use hydrophilic enrichment, high-resolution tandem mass spectrometry with complimentary and triggered fragmentation to profile Arabidopsis N-glycopeptides. A total of 492 N-glycosites were identified from 324 Arabidopsis proteins with extensive N-glycan structural heterogeneity revealed through 1099 N-glycopeptides. To demonstrate the precision of the approach, we also profiled N-glycopeptides from the β-1,2-xylosyltransferase mutant (xylt), an enzyme in the N-glycan biosynthetic pathway.