Ethyl carbamylated polyrotaxane (ECPR) and propyl carbamylated polyrotaxane (PCPR) were prepared based on the reactions between ethyl/propyl isocyanate and polyrotaxane (PR) in anhydrous DMSO under an argon atmosphere. By changing the alkyl type and substitution ratio, the PR derivative with good water-solubility was obtained and its solutions showed reversible sol–gel phase transition. During the heating process, transition temperature from sol to gel decreased from 32 °C to 18 °C with increasing the solution concentration from 2.44% to 13.5%, while in the cooling process, all the gels with various concentration did not turn into sols until the temperature decreased to 1 °C, exhibiting large hysteresis between heating and cooling.