Thermoplastic polyurethane (TPU) elastomers based on polyoxytetramethylene glycol (PTMG) with 2000 g.mol(-1) as soft segments (SSs) and isocyanates as well as their reaction with butanediol as hard segments (HSs) were synthesized. The three-dimensional supramolecular networks were constructed in TPU by the formation of physical HSs-rich domains via microphase separation, hydrogen bonding, and microcrystallization, which are dominated by the chemical structure of HSs. The robust stretchable TPU with an excellent tensile strength of 32 MPa and elongation of 1378% at break could be successfully prepared, and no crystallization happened to keep the elasticity even at a low temperature (-90 degrees C) when the steric semi-symmetric bis(4-isocyanatocyclohexyl)methane (HMDI) was introduced into HSs-rich domains. The crystallinity and ordered hydrogen bonding content decreased in HSs-rich domains with increases in steric hindrance and asymmetry of diisocyanates. A new approach was developed to construct the high-performance TPUs by introducing long PTMG SSs for the flexibility and elasticity and steric semisymmetric HMDI hard segments.