In this study, using ethylene carbonate and ethanolamine, we synthesized a novel diol chain-extender, bis-hydroxylethyl carbomate (EC-AE), which contains carbomate structure. The polyurethanes, PUA25 and PUB25, with different extenders, EC-AE and BDO, were synthesized by one-step polymerization, respectively. Their structures were characterized by using FT-IR and DSC. The results indicated that the microphase separation degree of PUA25 was less than that of PUB25, in other words, the amount of hydrogen bonding between hard segments and soft segments in PUA25 was superior to that in PUB25. And the formation of physically crosslinked hydrogels prepared by PUA25 and PUB25 were studied in detail. It was found that only PUA25 can form hydrogel in situ from solution state by cooling. And this kind of hydrogels showed the transition cycle of "gel-sol-gel" under "cooling-heating-cooling" thermal cycles, respectively. The results suggested that the physically crosslinked polyurethane hydrogels were easily possessed in high degree of phase mixing.