Aminoalcohols are extensively used in asymmetric syntheses. We use aminosugar derivatives in different fields, e.g. in reactions of formation and opening of oxazolidines, in the synthesis of chiral aminoalcohols, as substrates in the synthesis of new glycals. For this reason, we have synthesized a large number of N-alkyl and N,N-dialkyl derivatives of hexoses (Table 1), and have recorded their mass spectra using EI and CI techniques. In addition, high resolution (EI-HR) and metastable spectra have been recorded to support the proposed pathways of fragmentation. The ion structures proposed are partially speculative and can be considered merely as an aid in the visualization of pathways of fragmentation.