The composition and hard segment content of 13 commercial thermoplastic polyurethane elastomers (TPUs) were obtained using H-1-nuclear magnetic resonance (H-1-NMR). The properties of the TPUs were studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), dynamic mechanical thermal analysis (DMTA), and contact angle measurements. Solvent-based adhesives were prepared by dissolving the TPUs in 2-butanone. Films of the TPUs were obtained by solvent evaporation, and their properties were studied. Adhesion properties were determined from T-peel tests on solvent-wiped poly(vinyl chloride) (PVC)/polyurethane adhesive joints. The influence of the segmented structure on the properties of the TPUs was assessed. The increase in the hard segment content in TPUs favoured the incompatibility (i.e. reduced phase separation) between hard and soft domains. TPUs with a high hard segment content had a low crystallinity, a low wettability, and a high joint strength. The storage and loss moduli obtained using DMTA decreased as the hard segment content in the TPUs increased. Furthermore, the TPUs prepared using epsilon-polycaprolactone as the macroglycol had a slower crystallization rate than those prepared using the polyadipate of 1,4-butanediol or the polyadipate of 1,6-hexanediol. The increase in the length of the hydrocarbon chain of the macroglycol improved both the rheological and the thermal properties of the TPUs. Finally, TPUs prepared using MDI as the isocyanate showed a higher crystallinity and a higher degree of crosslinking than those prepared using TDI.