Ambient ionization of glycans is simply and efficiently achieved by spraying from an alkali metal salt-impregnated paper surface. Monosaccharides, oligosaccharides and ring glycans easily form abundant alkali metal adduct ions, and give simple and clean high-quality mass spectra. The enhancement is specific for glycans, compared to a wide variety of non-glycan compounds present in a matrix. In addition, molecular weight of unknown glycans can be further identified based on the ion mass difference of various alkali metal adduct ions from a certain compound when using a mixed salt-impregnated paper containing five cation salts. Successful determination of glycans and glycoconjugates in plant extracts, honey, blood and urine demonstrates the practicability of this approach to complicated matrices, especially biological matrices.