The molecular dynamics of water in mixtures with 5−66 vol% of glycerol was studied by measuring the spectrum of the velocity auto-correlation (VAS) in the frequency range from 50 Hz to 10 kHz with the NMR method of modulated gradient spin echo (MGSE). The ability of the method to follow the time evolution of VAS reveals the heterogeneity of molecular dynamics in water and its mixtures with low glycerol content attributed to the diﬀusion in the vortexes of hydrodynamic ﬂuctuations. By increasing the glycerol content, the spectrum exhibits a low-frequency peak that can be attributed to water clustered around a glycerol molecule. By taking into account the generalized Stokes-Einstein formula the form of VAS exposes the shear-thickening viscosity of mixtures, a possible mechanism behind the spontaneous folding of disordered poly-peptides into biologically active protein molecules. Results show that a low glycerol concentration only partially disrupts the hydrogen network of water and its molecular dynamics, but a higher glycerol completely changes the structure and dynamics in mixtures. In glycerol concentrations equal or higher than 10 vol% a new form of VAS develops, which conﬁrms the existence of hydro-clusters formed around hydrophilic glycerol molecules. This strongly inﬂuences the dynamics of surrounding water molecules. Viscosity of such mixture inhibits the rapid movement of water molecules and thus protects the macro-molecule against collisions that would prevent the formation of its own structure.