The glass transition temperature (Tg), density, refractive index, Raman scattering spectra, and X-ray photoelectron spectra (XPS) for xZnO–yBi2O3–zB2O3 glasses (x=10–65, y=10–50, z=25–60 mol%) are measured to clarify the bonding and structure features of the glasses with large amounts of ZnO.