Oligobutadiene-based prepolymers and polyurethanes (PU) were prepared from hydroxyl terminated polybutadiene (HTPB), three diisocyanates (aromatic, alicyclic and aliphatic) and two chain extenders (containing hydroxyl or amino groups). The free NCO content in the prepolymers varied systematically and the characteristic of these products were interpreted in terms of NCO group reactivity, propagation reactions and HTPB functionality. The mechanical properties of the polyurethane elastomers derived from the prepolymers were discussed in terms of hard and soft segment structures.