The structural relaxation properties of high-solid gelling polysaccharides, gelatin and whey protein with small-molecule co-solute have been reviewed focusing on the glass transition region and glassy state of the mechanical master curve. Compliance with the principle of thermorheological simplicity is established allowing horizontal superposition of viscoelastic functions in the form of small-deformation stress relaxation or dynamic oscillation modulus. Numerical calculations via the Tikhonov regularization yield smooth stress relaxation spectra over a broad timescale that encompasses the isothermal process of vitrification in these systems. Next, the molecular coupling theory addressed the polymer chain dynamics of the local segmental motions that determine the glass transition temperature (T g ) of condensed matrices. Thus a more complete picture of the physics of intermolecular interactions in the short-time region of the glass dispersion has emerged. It allows estimation of the relaxation time for local segmental motions at T g , and the extent of cooperativity between adjacent chemical moieties governing kinetics of viscoelastic relaxation in hydrocolloid based systems at the glass transition region.