In this study, poly(thiourethane) (PTU) with different structures is synthesized by click chemistry from trimethylolpropane tris(3-mercaptopropionate) (S3) and different diisocyanates (hexamethylene diisocyanate, HDI, isophorone diisocyanate, IPDI and toluene diisocyanate, TDI). Quantitative analysis of the FTIR spectra reveals that the reaction rates between TDI and S3 are the most rapid, resulting from the combined influence of conjugation and spatial site hindrance. Moreover, the homogeneous cross-linked network of the synthesized PTUs facilitates better manageability of the shape memory effect. All three PTUs exhibit excellent shape memory properties (Rrand Rfare over 90%), and an increase in chain rigidity is observed to negatively impact the shape recovery rate and fix rate. Moreover, all three PTUs exhibit satisfactory reprocessability performance, and an increase in chain rigidity is accompanied by a greater decrease in shape memory and a smaller decrease in mechanical performance for recycled PTUs. Contact angle (<90°) and in vitro degradation results (13%/month for HDI-based PTU, 7.5%/month for IPDI-based PTU, and 8.5%/month for TDI-based PTU) indicate that PTUs can be used as long-term or medium-term biodegradable materials. The synthesized PTUs have a high potential for applications in smart response scenarios requiring specific glass transition temperatures, such as artificial muscles, soft robots, and sensors.