The excited-state behavior of a select group of highly enantioenriched tri- and tetracyclic 2-cyclopentenones has been examined in two solvents. Prepared by a convergent pathway involving the coupling of cyclopentenyl bromide 12 to several chiral ketones followed by desilylation, perruthenate oxidation, and ring-closing metathesis, the reactants were conveniently irradiated through quartz. Following promotion to the triplet level, a cyclopropylcarbinyl biradical intermediate is presumably generated provided that the double bond linked to C4 is not saturated. Four pathways have been observed to operate, only one of which has been observed previously under rather different conditions. The new photorearrangements include non-Norrish fragmentation to a ketene, generation of a spirocyclic intermediate, and ring expansion to a cyclobutyl radical in advance of intramolecular fragmentation of the four-membered ring. In the latter instance, a hydrozulenone derivative is formed. In the majority of the examples, product structure and absolute stereochemistry were corroborated by means of X-ray diffraction analysis.