The release of sub-picomole levels of N-linked oligosaccharides directly from 1-5 micrograms of protein in a band on an SDS PAGE gel, coupled with recent advances in mass spectrometry and HPLC, opens the way for the analysis of biologically important glycoproteins that are difficult to purify or are available only in limited amounts. A straightforward HPLC strategy enables the structures of both neutral and sialylated components of the N-glycan pool to be predicted from a single run. The entire pool of sugars may then be sequenced simultaneously, using exoglycosidase arrays.