Automated electrochemical assembly, which is an electrochemical method for automated solution-phase synthesis of oligosaccharides, has been developed. The method is an enabling tool for preparation of chitooligosaccharides and their derivatives as biologically active middle-sized molecules. Electrochemical activation is useful to synthesize cyclic oligosaccharides and is combined with ionic liquid tag strategy to facilitate analysis and purification of synthesized oligosaccharides.