Stable isotopic labeling dramatically facilitates NMR studies of oligosaccharides. We previously established a method for overexpressing homogeneous high-mannose-type oligosaccharides with metabolic C-13 labeling using genetically engineered yeast cells. To extend the applicability of this methodology, we combined it with chemoenzymatic synthesis using a specific glucosyl transferase. Our hybrid approach has enabled the production of a uniformly and selectively C-13-labeled dodeca-saccharide with terminal glucosylation, a signal recognized by molecular chaperones, providing useful NMR tools for detailed conformational analyses.