Mass spectrometry (MS) is a well-accepted means for analyzing glycans. Before glycan analysis by MS, several chemical derivatizations are generally carried out. These are classified into three categories; (1) labeling of the reducing end of glycans, (2) permethylation, and (3) sialic acid derivatization. Because sialic acid residues are unstable, they are easily lost during pretreatment and during or after ionization in a mass spectrometer. Sialic acid derivatization can prevent the loss of this residue. Recently, new types of sialic acid derivatization techniques have been developed, which allow straight-forward sialic acid linkage analysis (α2,3-/α2,6-linkages) as well as residue stabilization. This review summarizes the developments in sialic acid derivatization techniques, especially the varied methods of sialic acid linkage-specific derivatization.