Homogeneous ice nucleation was investigated in aqueous solutions of poly[ethylene glycol] (PEG) with a molar mass between 300 and 6000 g mol(-1). Experiments were performed with a differential scanning calorimeter using emulsified aqueous PEG solutions with concentrations of 0 - 44 wt %. Equilibrium phase transition temperatures are determined and discussed, in particular the simultaneous occurrence of metastable and stable eutectic temperatures. The observed homogeneous freezing temperatures of ice reveal a continuous increase in the supercooling of PEG solutions with increasing molar mass of the PEG. The freezing behavior was investigated within the framework of water-activity-based ice nucleation theory. The latter predicts that homogeneous ice nucleation in aqueous solutions is independent of the nature of the solute, but depends only on the water activity of the solution. Water activity data of various PEG solutions in the stable and supercooled range were compared. It was found that the water activity of PEG solutions decreases with decreasing temperature. This trend is stronger for the PEGs of larger molar mass, and can explain why solutions of larger PEGs supercool more readily. Our study shows that the predictions of water-activity-based ice nucleation theory are consistent with the observed freezing behavior and with the thermodynamic properties of PEG solutions. It is also in agreement with the suggestion of a thermodynamic control of ice nucleation in aqueous systems due to the existence of a liquid phase spinodal. (C) 2003 American Institute of Physics.