Differential scanning calorimeteric (DSC) heating thermograms of amorphous poly(N-vinyl pyrollidone) (PVP) blends with short-chain poly(ethylene glycol) (PEG) feature exotherms of cold crystallization coupled with symmetric melting endotherms, which relate to the state of the crystalline component, PEG, while PVP-PEG hydrogen-bonded complex reveals itself as an amorphous phase. As PEG content in blends exceeds a characteristic level, PEG cold crystallization occurs upon heating of the coal-quenched samples through their glass transition temperatures (T-g). The contributions of both thermodynamic and kinetic factors to the occurrence of non-crystallizable PEG have been analysed by considering the dependence of the PEG cold crystallization temperature, T-c, on blend T-g and composition along with the compositional dependence of the heat of melting of PEG. The stoichiometry of the PVP-PEG H-complex was evaluated from DSC thermograms as the amount of non-crystallizable PEG in PVP-underloaded blends. (C) 2000 Elsevier Science Ltd. All rights reserved.