Photodimerization of 3,5-diaryl-2-cyclohexenones (1) in benzene solution gave the dimers 3. “Head-to-tail” structures are assigned for 3 on the basis of spectroscopic studies and reasoning from molecular models. Photolysis of the 3-styryl derivatives (5) afforded bicyclo[4,2,0]octan-1,5-dienes (8).