Peptides containing phosphoseryl residues can be modified by removal of the phosphate groups via beta-elimination followed by addition of pyridoxamine to the resulting dehydroalanyl residue. Peptides containing the modified residues can be detected at nanomole levels by monitoring absorbance at 328 nm or at picomole levels by monitoring fluorescence. Photolysis of the modified peptide converts the pyridoxamino adduct to a form which can be readily identified after Edman degradation.