The photosensitized [2 + 2]-cycloaddition of chalcones, conjugated cyclopentenones, and cyclohexenones with electron-rich alkenes such as cyclic enolethers and polymethylated alkenes was investigated. While cyclic enones showed high regio- and stereoselectivity, acyclic enones resulted in a more complex product mixture containing dimers as well as four dominant regio- and diastereoisomers. This complex product mixture can be controlled by adjusting the reaction conditions such as sensitizer, solvents, or additives.