Three series of polyurethanes, based on three polyols, diphenylmethane diisocyanate (MDI), and three chain extenders were synthesized. Polypropylene glycol (PPG) soft-segment length (MW 1000, 2000, and 3000), soft-segment concentration (30%, 50%, and 70%), and the type of chain extender (ethylene glycol, butane diol, and hexane diol) were varied and their effect on the amount of phase separation studied. Methods for assessing phase separation quantitatively, based on shifts of the glass transition temperature Tg and the enthalpy jump at the glass transition were tested. It was shown that they give incorrect results, especially with PPG 1000 as the soft segment. Dependence of the soft segment Tg on the polyol length was explained by the “network effect.” True phase mixing was found only with PPG 1000 series at low soft-segment concentration, whereas, no clear indication of the phase mixing with PPG 2000 and PPG 3000 based polyurethanes was observed