A requirement for optimum performance in a pressure-sensitive adhesive (PSA) is the right balance between viscous and elastic properties, achieved by controlling the molecular architecture. Here, waterborne polyurethane PSAs are synthesized using a blend of polyether and polyalkene-based polyols. The effects of the polyol type and molecular weight on the adhesive and thermomechanical properties are explored to optimize them for PSA applications. A linear polyurethane is synthesized by the reaction of an aliphatic diisocyanate with a diol blend of polypropylene glycol (PPG) and hydroxyl-terminated polybutadiene (HTPB). With increasing concentrations of flexible HTPB segments and the associated increased viscous dissipation a favorable increase in the tack adhesion energy and peel strength is obtained. Adhesive properties are improved with increasing PPG molecular weight because chain entanglements become possible in the soft segments and raise the storage modulus.