Thermoplastic polyurethanes are frequently used in daily life. However, their endurance of the large strain stretch is poor, just like other thermoplastic polymers. Most of them could only recover to ~88% of its initial length after 500% or larger elongation. We found that the addition of non-planar rings in the hard segment of polyurethanes, which will depress the hydrogen bonding associations, could surprisingly and largely improve the recovery ratio of polyurethanes, even after their break during stretch. Such phenomenon is closely related to the non-planar ring structure and their multi-scale effect on mechanical properties has been investigated by sing-molecule force spectrum, infrared spectroscopy, X-ray scattering and DMA etc. It is found that the incorporation of non-planar ring could decrease the elastic modulus of the single chain seriously, and the degree of micro-phase separation is deteriorated too. In contrary to the traditional physical image, the recovery ratio is impressively enhanced from ~85% to 99%.