Two series of polyether polyurethanes based on hydroquinone bis(beta-hydroxyethy) ether (HQEE) or 1,4-butanediol (BDO) as a chain extender were prepared by a one-step bulk polymerization process. Their hydrogen bonding and morphological structure were studied by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Compared with BDO-based polyurethanes, HQEE-based polyurethanes showed better phase segregation and higher extent of ordering in the hard domain. Besides short-range hydrogen bonds, a considerable amount of long-range hydrogen bonds existed in amorphous phase of the hard domain. The soft segment was easier to crystallize, and the melting temperature of the hard domain was elevated in HQEE-based polyurethanes. Its hard domain displayed a banded structure, rather than spherulitic structure in BDO-based polyurethanes.