We studied the mass spectrometric behaviour of peracetylated and underivatized anomeric hexopyranosyl azides and 5-thioglucopyranosyl azides by means of different mass spectrometric techniques. The unstable molecular ions fragment predominantly by losing either N3 radical or N2 molecule. Loss of N2 molecule and the protonation of the derived nitrene were characteristic of the studied compounds. The presence of BF3.Et2O in the ion source is favorable for producing the protonated nitrene form. The protonated nitrene shows a new type of ring expansion rearrangement. The abundances of the [M + H - N2]+ ion makes it possible to identify the anomeric configuration of the azido group.