Different multiple hard segment polyurethane-imide copolymers (MHPUI) were synthesized and characterized. FTIR spectroscopy confirmed the characteristic absorption of the MHPUI copolymer. The difference in the imide group FTIR absorption bands in different MH segment PUI copolymers was found in this study and was explained by the different MH segment types, hard segment contents, and hard segment rigidity with different interactions of the molecular chains. The hard segment interaction in MHPUI with an increase of the structure rigidity of the short hard segments is strengthening. The DSC analysis revealed that the glass-transition temperature of the soft segment of PUI rose in value from -42 to -3.4degreesC with the introduction of MH and different TMH segments. The DSC results suggest that the soft segment is more compatible with the hard segment rigidity increase. The TGA results showed the hard segment structure symmetry has a more important role in the MHPUI thermal stability. Every sample containing symmetrical structure short hard groups (4,4'-diphenylmethane diisocyanate or 4,4'-diaminodiphenylmethane) is more thermally stable than that with worse symmetry structure groups (2,4-toluene diisocyanate or 3,3'-diamino-4,4'-diaminodiphenylmethane). The three-step mechanism of PUI thermal degradation was further verified by the TGA study. The thermally unstable group was confirmed as urethane or a urea-urethane segment. The TGA results showed that MHPUI copolymers with higher separation of the soft-hard phase have higher thermal stability.