Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4'-diisocyanate) and polyadipate of 1,4-butanediol (M-w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1: 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.