AbstractThe effect of polymeric molecular weight and molecular weight distribution on pressure‐sensitive adhesive performance was studied in a model system of commercial polyisobutylenes. Molecular weight was characterized by size exclusion chromatography and membrane osmometry. Pressure sensitive adhesive performance was assessed by shear, peel, and probe tack testing based on standardized test methods. Lower molecular weight polyisobutylenes (Mw<600,000) are successful in peel and probe tack testing due to their ability to flow quickly and wet the substrate test surface. They do not function as well in shear, however, where the polymer must resist flow under a load. High molecular weight species, by contrast, perform well in shear resistance tests and less successfully in peel and probe tack testing. Where high and low molecular weight polyisobutylenes are blended to broaden the molecular weight distribution while maintaining constant weight average molecular weight, adhesive performance in shear, peel, and probe tack are improved. All of the adhesive properties tested were found to have their foundation in some fundamental rheological properties of the polymers (e.g., shear viscosity and tensile creep compliance). This suggests the use of fundamental rheological characterization for screening of adhesive formulations over more empirical adhesive testing method