The cucurbit[8]uril (CB8) templation strategy that is known to yield stereoselective photodimers of organic olefins has been extended to substituted butadienes. By virtue of its strong binding interactions with guests the rigid cavity of CB8 is capable of preorienting the diene guests to result in greater yields of stereoselective photodimers upon irradiation. The symmetry of the butadiene monomers influences the relative arrangement of the monomers in complexes leading to the observed product selectivity.