Ultraviolet (UV) irradiated suprarnolecular polybutadienes (PBs) containing 2-ureido-4-[1H]-pyrimidone (UPy) linkages were examined as a simple model for curable supramolecular elastomers. Via precise control of UV exposure, the cure and the degradation of the vinyl groups within the PB elastomeric core were investigated. The combination of UPy binding and covalent cross-linking by UV irradiation dramatically enhanced mechanical properties of these UPy-functionalized elastomers, yielding toughness enhancement up to similar to 200x at the 5 min UV cure. UV-initiated cross-linking dominated the curing process up to similar to 50 min exposure time. Beyond this cure time, dominant degradation of the vinyl linkages was observed. Control of this UV-initiated process yielded supramolecular elastomers with a covalently cross-linked phase induced by UV irradiation combined with a noncovalent UPy cross-linked phase induced by secondary hydrogen bonding interactions. Of particular note, it was determined that the presence of UPy hydrogen-bonded aggregates accelerated the UV cross-linking process during the initial stage of exposure. This observation was attributed to rnicrophase-separated structure of UV-irradiated supramolecular elastomer, where UPy aggregation increased the probability of interaction between the pendant vinyls responsible for UV cross-linking. The systematic study of uniaxial tensile behavior of the UV-irradiated supramolecular elastomers offers new insight into the design and architecture of mechanically tunable supramolecular elastomers.