In this study, when deriving thermoplastic polyurethane (TPU), the researchers replaced 1,4-butanediol (1,4-BDO) with 1,3-butanediol (1,3-BDO) as a chain extender and examined how the structure of the chain extender affected the final polymers. Regarding the raw materials for polymerization, three types of commercial polyols with the same molecular weight (Mn = 1000 g/mol), namely, poly (butyl acrylate) (PBA), poly (tetramethylene ether) glycol (PTMG), and polycarbonate diol (PCDL) were used. These polyols were used in conjunction with butanediol and 4,4’-methylene diphenyl diisocyanate. Three groups of TPUs were successfully synthesized using one-shot solvent-free bulk polymerization. Compared with TPUs polymerized using 1,4-BDO, materials polymerized using 1,3-BDO are more transparent and viscous. Structural analysis revealed that no substantial differences between the final structures of the TPUs were present when different chain extenders were used. Thermal analysis indicated that compared with TPUs polymerized using 1,4-BDO, the glass transition temperature of those with 1,3-BDO was 15 °C higher. Examination of microphase separation in the structure by using morphological analysis revealed that compared with TPUs synthesized using 1,4-BDO, PBA, and PTMG synthesized using 1,3-BDO were relatively separated. PCDL synthesized using 1,3-BDO exhibited no morphological difference. Rheological analysis indicated PCDL synthesized using either 1,4-BDO or 1,3-BDO did not exhibit any obvious differences. In conclusion, TPUs synthesized using PCDL and 1,3-BDO exhibited thermal plasticity at room temperature (15–20 °C). Their basic application could be extended to the development of smart materials. In terms of further application, they could be used in shape memory and temperature-sensitive high molecular polymers.